Color-photographic recording material for the silver dye bleach process

ABSTRACT

A color-photographic recording material for the silver dye bleach process, which contains oil-soluble azo dyes of the formula ##STR1## in which R 1  is hydrogen, alkyl, alkoxy, alkenyl, acyl, carbalkoxy, acylamino, carbamide, sulfonamide, alkylsulfone, arylsulfone, aryloxy, arylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R 2  is hydrogen, alkyl, alkoxy, carbalkoxy, carbamide, sulfonamide, alkylsulfone, arylsulfone, aryloxy, cyano, nitro or halogen, R 3  is hydrogen, alkyl, alkoxy, phenoxy, sulfonamide, alkylsulfone, sulfonic acid ester, cyano, nitro, halogen, carbalkoxy, carbamide or phosphoric acid diester, R 4  is hydrogen, alkyl, alkoxy, carbalkoxy, carbamide, sulfonamide, acylamino, alkylsulfone, arylsulfone, hydroxyl, cyano, nitro or halogen, R 5  is hydrogen, alkyl or carbalkoxy, X 1  is hydrogen, alkyl, alkoxy, acylamino, alkylsulfonamide or hydroxyl, Y 1  is hydrogen, alkyl, alkoxy, amino, carbalkoxy, arylsulfonamide, acylamino, halogen, hydroxyl or phosphamic acid ester, Z 1  is hydrogen, alkyl, alkoxy, acylamino, acyl, carbalkoxy, alkylsulfonamide or halogen or forms a ring with Y 1 , and W 1  is hydrogen, alkyl, alkoxy or halogen. The substituents mentioned can, where relevant, themselves be further substituted. 
     The oil-soluble azo dyes are easily incorporated into silver halide gelatin emulsions and are very stable therein. Because of the good oil-solubility of the azo dyes, very thin layers can be cast in producing photographic materials, and this has an advantageous effect on, for example, the image sharpness.

The present invention relates to a colour-photographic recording material for the silver dye bleach process, which contains at least one diffusion-resistant, bleachable and oil-soluble monoazo dye in at least one silver halide emulsion layer or in a colloid layer adjoining a silver halide emulsion layer.

The use of water-soluble polyazo or azoxy dyes for the silver dye bleach process is known (A. Meyer, J. Phot. Ser. 13, (1965), 90; Research Disclosure 17643/VII A, December 1978). An immediate advantage of the use of such azo dyes is that it permits easy and homogeneous dyeing of the hydrophilic, colloidal binders of a photographic layer, especially of gelatin. Furthermore, in the course of processing exposed silver dye bleach materials, water-soluble cleavage products or azo dyes, which can easily be washed out, are produced in the image areas. Amongst the disadvantages which arise when using water-soluble azo dyes, however, the tendency of these days to diffuse into and between photographic layers is particularly important. It has already been proposed to use reactive dyes to overcome this disadvantage. This however had too great an effect on the rheological, chemical and mechanical properties of the photographic layer to be produced. The use of water-soluble azo dyes of higher molecular weight also did not give a completely satisfactory result. It is true that it increased the diffusion resistance, but the tendency of such dyes to form micelles by aggregation is a further disadvantage, which significantly interferes with rheological properties of the coating solution and the colour density of the photographic image.

Swiss Pat. No. 600,385 describes a silver dye bleach process, in which water-insoluble azo dyes having blocked auxochromes are dispersed in gelatin. However, these dyes bleach only very slowly, and incompletely. Furthermore, the regeneration of the desired image dye requires a special treatment in a strongly alkaline medium. Other water-insoluble azo dyes, which have been incorporated into silver dye bleach materials, are difficult to prepare and show too low a stability to changes in pH value, and to the action of light (U.S. Pat. No. 3,544,326; Research Disclosure 14983, September 1976).

Accordingly, it is the object of the present invention to provide novel photographic recording materials for the silver dye bleach process, which employ water-insoluble dyes which are easily incorporated into the layers of the recording materials and which, because of their fastness characteristics, lead to a material which gives images of improved quality.

Oil-soluble azo dyes, for use in photographic layers of silver dye bleach materials, have now been found, which impart the desired properties to the recording material and give high-quality photographic images.

Accordingly, the present invention relates to a colour-photographic recording material for the silver dye bleach process, which contains at least one diffusion-resistant, bleachable and oil-soluble monoazo dye in at least one silver halide emulsion layer or in a colloid layer adjoining the silver halide emulsion layer, and wherein the dye has the formula ##STR2## in which R₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, substituted or unsubstituted alkoxy having 1 to 16 carbon atoms, substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, substituted or unsubstituted aliphatic acyl having 2 to 5 carbon atoms, substituted or unsubstituted benzoyl, substituted or unsubstituted carbalkoxy having 2 to 20 carbon atoms or --NV₁ COU₁, in which V₁ is hydrogen or alkyl having 1 to 4 carbon atoms and U₁ is substituted or unsubstituted alkyl having 1 to 12 carbon atoms or substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, or R₁ is N-alkyl-substituted or N,N-dialkyl-substituted carboxamido or sulfonamido, in which each alkyl moiety has 1 to 12 carbon atoms and can be substituted further, or R₁ is substituted or unsubstituted alkylsulfone having 1 to 12 carbon atoms, substituted or unsubstituted arylsulfone, substituted or unsubstituted aryloxy or substituted or unsubstituted arylsulfonic acid ester, or is hydroxyl, cyano, nitro or halogen, R₂ is hydrogen, substituted and unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted, or R₂ is substituted or unsubstituted alkylsulfone having 1 to 6 carbon atoms, substituted or unsubstituted arylsulfone or substituted or unsubstituted aryloxy, or is cyano, nitro or halogen, R₃ is hydrogen, substituted or unsubstituted alkyl or alkoxy having 1 to 4 carbon atoms, substituted or unsubstituted phenoxy, or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted, or R₃ is substituted or unsubstituted alkylsulfone having 1 to 4 carbon atoms, substituted or unsubstituted phenylsulfonic acid ester, cyano, nitro, halogen, substituted or unsubstituted carbalkoxy having 1 to 16 carbon atoms, or --P(O)(OT¹)₂, in which T¹ is alkyl having 1 to 4 carbon atoms, R₄ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 16 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 12 carbon atoms and can be substituted, or R₄ is --NQ₁ COT₁, in which Q₁ is hydrogen or alkyl having 1 or 2 carbon atoms and T₁ is substituted or unsubstituted alkyl having 1 to 4 carbon atoms, or R₄ is substituted or unsubstituted alkylsulfone having 1 to 12 carbon atoms, substituted or unsubstituted arylsulfone, hydroxyl, cyano, nitro or halogen, R₅ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms or substituted or unsubstituted carbalkoxy having 2 to 13 carbon atoms, X₁ is hydrogen, substituted or unsubstituted alkyl or alkoxy having 1 to 6 carbon atoms or --NL₁ CO-M₁, in which L₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 4 carbon atoms and M₁ is substituted or unsubstituted alkyl or alkoxy having 1 to 24 carbon atoms, or X₁ is substituted or unsubstituted alkylsulfonylamino having 1 to 25 carbon atoms or hydroxyl, Y₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 12 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted, or Y₁ is substituted or unsubstituted arylsulfonylamino or --NE₁ COG₁, in which E₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 8 carbon atoms and G₁ is substituted or unsubstituted alkyl having 1 to 12 carbon atoms or substituted or unsubstituted alkoxy having 1 to 4 carbon atoms, or Y₁ is --NE₁ P(O)(OG¹)₂, in which E₁ is as defined above and G¹ is alkyl having 1 to 12 carbon atoms, or Y₁ is halogen or hydroxyl, Z₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms or --NA₁ COD₁, in which A₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 8 carbon atoms and D₁ is substituted or unsubstituted alkyl having 1 to 18 carbon atoms, or Z₁ is substituted or unsubstituted acyl having 2 to 9 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 19 carbon atoms, substituted or unsubstituted alkylsulfonylamino having 1 to 6 carbon atoms, halogen or the atoms which together with Y₁ form a substituted or unsubstituted 5-membered or 6-membered, saturated or unsaturated ring which can contain 1 or 2 hetero-atoms, and W₁ is hydrogen, substituted or unsubstituted alkyl or alkoxy, each having 1 to 4 carbon atoms, or halogen.

The invention further relates to the process of preparation of the photographic recording material, to the use of the material for the production of photographic images and to the process for the production of photographic images using silver dye bleach materials which contain the oil-soluble azo dyes according to the invention in the photographic layers.

The substituent R₁ is, for example, hydrogen, or alkyl which has 1 to 18 carbon atoms and can be straight-chain or branched. Examples of such alkyl radicals are methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert.-butyl, amyl, tert.-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, 1-methylethylpentyl, hexyl, 1-methylpentyl, neopentyl, 1-, 2- and 3-methylhexyl, heptyl, n-octyl, tert.-octyl, 2-ethylhexyl, n-nonyl, isononyl, tert.-nonyl, decyl, tert.-decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and the corresponding isomers.

Alkyl radicals having 1 to 12 carbon atoms are preferred, and those having 1 to 6 carbon atoms are particularly preferred. They can be substituted by carbalkoxy having 2 to 12, especially 2 to 6, carbon atoms. An alternative possible substituent is alkoxy having 1 to 4 carbon atoms.

If R₁ is alkoxy having 1 to 16 carbon atoms, it can be an alkoxy radical analogous to the alkyl radicals mentioned. Alkoxy radicals having 1 to 8 carbon atoms are preferred. A possible substituent of the alkoxy radicals is --OC₂ H₄)_(n) O(CH₂)_(m) CH₃, in which n is 1 or 2 and m is an integer from 0 to 3.

R₁ can also be alkenyl having 2 to 4 carbon atoms, and especially vinyl. Substituents for these unsaturated radicals include cyano and carbalkoxy having 2 to 9 carbon atoms. One or both of these substituents can be present on an alkenyl radical.

R₁ can also be an aliphatic or aromatic (carboxylic acid) acyl radical. If R₁ is aliphatic acyl, it has 2 to 5 carbon atoms and can be substituted by methoxy or ethoxy. Acyl having 2 or 3 carbon atoms is preferred, and acetyl is particularly preferred. If R₁ is an aromatic acyl, it is preferably benzoyl, which can have additional substituents in the para-position, for example chlorine, --CO₂ B, --SO₂ B or --COB, in which B is alkyl having 1 to 8, especially 1 to 4, carbon atoms.

If R₁ is carbalkoxy, the alkoxy moiety has 1 to 19 carbon atoms. Alkoxy having 1 to 16, especially 1 to 8, carbon atoms is preferred. These alkoxy moieties correspond to the alkyl radicals mentioned. Examples of substituents of the said alkoxy moieties are --OC₂ H₄)_(n) OCH₃ and --OC₂ H₄)_(n) OC₂ H₅ in which n is as defined above.

If R₁ is ##STR3## V₁ can be hydrogen or alkyl having 1 to 4 carbon atoms, hydrogen being preferred. U₁ is alkyl having 1 to 12, preferably 1 to 8, especially 1 to 4, carbon atoms, which can be substituted by methoxy or hydroxyl. U₁ can also be alkenyl having 2 to 4 carbon atoms.

R₁ is carboxamido of the formula --CONH₂ or sulfonamido of the formula --SO₂ NH₂. It can also be N-alkyl-substituted or N,N-dialkyl-substituted carboxamido or sulfonamido, in which each alkyl moiety has 1 to 12, especially 1 to 10, and preferably 1 to 5, carbon atoms. Examples of possible substituents of the alkyl radicals are methoxy, hydroxyl and amino.

The substituent R₁ can also be alkylsulfone having 1 to 12, especially 1 to 8, and particularly preferably 1 to 6, carbon atoms. The alkyl moiety can be substituted further, for example by methoxy, ethoxy or hydroxyl.

If R₁ is arylsulfone, the preferred meaning is phenylsulfone, which can be substituted by alkyl having 1 to 5 carbon atoms or hydroxyl, preferably in the paraposition. The same substitution is possible if R₁ is aryloxy, preferably phenoxy, or an arylsulfonic acid ester group, especially a phenylsulfonic acid ester group.

R₁ can also be hydroxyl, cyano, nitro or halogen; in the last-mentioned case, chlorine and bromine are preferred.

The substituent R₂, which is in the ortho-position to the azo group, is, for example, hydrogen or alkyl having 1 to 12 carbon atoms. Suitable alkyl radicals are the relevant radicals mentioned for R₁, alkyl radicals having 1 to 8 carbon atoms being preferred, and methyl being especially preferred. The alkyl radicals can be substituted by halogen, especially by fluorine.

If R₂ is alkoxy having 1 to 6 carbon atoms, particularly preferred meanings are methoxy and ethoxy; such radicals can be substituted by further methoxy groups.

R₂ can also be carbalkoxy having 2 to 5, especially 2 or 3, carbon atoms; the alkoxy moiety can be substituted, for example by methoxy.

R₂ can also be N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which groups each alkyl moiety has 1 to 8, preferably 1 to 4, carbon atoms; these alkyl moieties can be substituted by methoxy.

A further meaning of R₂ is alkylsulfone having 1 to 6, especially 1 to 4, carbon atoms; it can be substituted by, for example, methoxy or hydroxyl.

If R₂ is arylsulfone, a particularly preferred meaning is phenylsulfone, which can be substituted further by alkyl having 1 to 5 carbon atoms.

If R₂ is aryloxy, a preferred meaning is phenoxy. Aryloxy can be substituted by, for example, alkyl having 1 to 8, especially 1 to 5, carbon atoms, the substituent preferably being in the para-position of the aryl moiety.

R₂ can also be cyano, nitro or halogen; in the last-mentioned case, chlorine and bromine are preferred.

The substituent R₃, which is also in the ortho-position to the azo group, can be, for example, hydrogen or alkyl. If it is alkyl, it has 1 to 4 carbon atoms, methyl being preferred, and can be substituted by methoxy.

If R₃ is alkoxy, it has 1 to 4 carbon atoms and can be substituted by methoxy.

R₃ can also be phenoxy, which can be substituted by halogen, especially by chlorine.

If R₃ is N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, each alkyl moiety in these groups can be one of those mentioned above, having 1 to 6, preferably 1 or 2, carbon atoms. Preferably, the nitrogen atom of the sulfonamido or carboxamido radical has two alkyl substituents, which can be further substituted by methoxy.

If R₃ is alkylsulfone, the alkyl moiety has 1 to 4 carbon atoms; methylsulfone is preferred.

If R₃ is a phenylsulfonic acid ester group, it can be substituted by alkyl having 1 to 5 carbon atoms.

R₃ can also be cyano, nitro or halogen, and in the last-mentioned case chlorine and bromine are particularly preferred.

If R₃ is carbalkoxy, the alkyl moiety has 1 to 16, especially 1 to 12, preferably 1 to 6, carbon atoms, and can be substituted by methoxy or ethoxy.

If R₃ is --P(O)(OT¹)₂, T¹ is alkyl having 1 to 4 carbon atoms, especially 1 or 2 carbon atoms.

The substituent R₄ can be, for example, hydrogen or alkyl having 1 to 4 carbon atoms; a preferred meaning of alkyl is methyl. The alkyl radicals can be substituted by hydroxyl or halogen, especially fluorine.

If R₄ is alkoxy having 1 to 6, especially 1 or 2, carbon atoms, the radicals can be further substituted by methoxy.

R₄ can also be carbalkoxy having 2 to 16 carbon atoms. Preferably, the alkyl moiety has 2 to 9 carbon atoms. Examples of suitable substituents on the alkyl moiety are methoxy, ethoxy and --OC₂ H₄ --OCH₃.

R₄ can also be N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which groups each alkyl moiety has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and especially 1 or 2 carbon atoms. The alkyl moieties can be substituted by methoxy.

If R₄ is ##STR4## Q₁ is hydrogen or alkyl having 1 or 2 carbon atoms, hydrogen being preferred, and T₁ is alkyl having 1 to 4 carbon atoms. The alkyl radicals Q₁ and T₁ can be substituted by hydroxyl, cyano, chlorine or bromine.

If R₄ is alkylsulfone, the alkyl moiety can have 1 to 12, especially 1 to 6, carbon atoms, and the most preferred meaning is methyl. The alkyl moieties can be substituted by amino.

If R₄ is arylsulfone, a preferred meaning is phenylsulfone. Suitable substituents are alkyl radicals having 1 to 5 carbon atoms, and are preferably in the para-position of the aryl radicals.

R₄ can also be hydroxyl, cyano, nitro or halogen, of which hydroxyl, cyano and chlorine are particularly suitable.

The substituent R₅ can especially be hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl. The alkyl radicals can be substituted by carbalkoxy having 2 or 3 carbon atoms.

R₅ can also be carbalkoxy having 2 to 13 carbon atoms in the alkyl moiety, preferably 2 to 7 carbon atoms and especially 2 or 3 carbon atoms. A suitable substituent of the alkyl moiety is methoxy.

The substituent X₁ can be, for example, hydrogen, or alkyl or alkoxy, each having 1 to 6, especially 1 to 4, carbon atoms. If X₁ is alkoxy, a preferred meaning is methoxy. The alkyl and alkoxy radicals can be substituted by, for example, hydroxyl or methoxy.

X₁ can also be ##STR5## in which L₁ is hydrogen or alkyl having 1 to 4 carbon atoms, methyl being preferred, and M₁ is alkyl or alkoxy having 1 to 24 carbon atoms. The alkyl radicals can be any of the isomers mentioned as examples of the substituent R₁ being alkyl, and can in addition be the straight-chain alkyl radicals having 19, 20, 22 or 24 carbon atoms. The same applies to the alkoxy radicals. Preferred alkyl radicals have 1 to 13, especially 1 to 8, carbon atoms. Preferred alkoxy radicals have 1 to 4 carbon atoms, and methoxy and ethoxy are particularly preferred. Substituents of the alkyl and alkoxy radicals can be fluorine, chlorine, carbalkoxy having 2 to 5, preferably 2 or 3, carbon atoms, phenyl, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --, phenoxy,para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O--, m₃ being an integer from 1 to 8, or alkoxy having 1 to 5 carbon atoms.

If X₁ is alkylsulfonylamino (--NHSO₂ -alkyl), the alkyl moiety contains 1 to 25 carbon atoms, preferably 1 to 12, and especially 1 to 6, carbon atoms. Examples of possible substituents of the alkyl moiety are methoxy, cyano and phenyl.

X₁ can also be hydroxyl.

The substituent Y₁ can be, for example, hydrogen or alkyl having 1 to 6 carbon atoms, preferably methyl or ethyl.

Suitable alkoxy radicals Y₁ have 1 to 12, especially 1 to 8, carbon atoms, and can be further substituted by methoxy, ethoxy or radicals of the formula --OC₂ H₄ OCH₃ or --OC₂ H₄ OC₂ H₅.

If Y₁ is carbalkoxy having 2 to 5, especially 2 or 3, carbon atoms, it can for example be substituted by alkoxy groups, such as --OC₂ H₄ --OCH₃.

Y₁ can also be N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6, especially 1 to 4, carbon atoms. The alkyl moieties can be substituted by methoxy, carbalkoxy having 2 to 5 carbon atoms, acetoxy, hydroxyl, nitro, cyano, phenyl or tosyl. Amino Y₁ can also be cyclic amino, for example pyrrolidinyl, piperidinyl or morpholinyl.

If Y₁ is arylsulfonylamino (--NHSO₂ -aryl) a preferred meaning is phenylsulfonylamino. A suitable substituent is alkyl having 1 to 4 carbon atoms.

If Y₁ is ##STR6## E₁ is hydrogen or alkyl having 1 to 8, especially 1 or 2, carbon atoms. The alkyl radicals can be substituted by cyano. G₁ can be alkyl having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and can be substituted by methoxy or ethoxy. G₁ can also be alkoxy having 1 to 4 carbon atoms, especially methoxy or ethoxy. The alkoxy radicals can be substituted by --OC₂ H₄)_(n) OCH₃, where n is as defined above.

If Y₁ is --NE₁ P(O)(OG¹)₂, E₁ is as defined above, G¹ is alkyl having 1 to 12, especially 1 to 6, preferably 1 to 4, carbon atoms.

Y₁ can also be halogen or hydroxyl, chlorine being the preferred halogen.

The substituent Z₁ is, for example, hydrogen or alkyl having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms. The alkyl radicals can be substituted by hydroxyl, halogen or cyano.

If Z₁ is alkoxy having 1 to 6, especially 1 to 4, carbon atoms, the alkoxy radical can be substituted by --O(CH₂)_(m) --CH₃, in which m is 0, 1, 2 or 3.

Z₁ can also be ##STR7## in which A₁ is hydrogen or alkyl having 1 to 8 carbon atoms, preferably methyl, and D₁ is alkyl having 1 to 18 carbon atoms, preferably 1 to 12 and especially 1 to 8 carbon atoms. The alkyl radicals can be substituted by hydroxyl or amino.

Z₁ can also be (carboxylic acid) acyl having 2 to 9, especially 2 to 5, carbon atoms, acetyl being particularly suitable. Acyl can be substituted by methoxy.

If Z₁ is carbalkoxy, the alkyl moiety has 1 to 18, preferably 1 to 12, carbon atoms, and can be substituted by --OC₂ H₄)_(n) OCH₃, in which n is as defined above.

Z₁ can also be alkylsulfonylamino, in which the alkyl moiety contains 1 to 6 carbon atoms and is preferably methyl.

If Z₁ is halogen, chlorine is particularly preferred.

Z₁ can also be the atoms which together with Y₁ form a 5-membered or a 6-membered, saturated or unsaturated ring which can contain one or two hetero-atoms. Suitable hetero-atoms are nitrogen and oxygen, and either one or both of these can be present. The rings can be substituted by methyl. Examples are ##STR8##

The substituent W₁ can be hydrogen or alkyl or alkoxy, each having 1 to 4 carbon atoms, and methyl, methoxy, ethyl and ethoxy being preferred. The alkyl or alkoxy radicals can be substituted by methoxy.

If W₁ is halogen, the preferred meaning is chlorine.

Preferred oily-soluble azo dyes for use in photographic layers of silver dye bleach materials are those of the formula ##STR9## in which R₆ is hydrogen, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 16 carbon atoms, substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, substituted or unsubstituted aliphatic acyl having 2 or 3 carbon atoms, substituted or unsubstituted benzoyl, substituted or unsubstituted carbalkoxy having 2 to 16 carbon atoms, or --NV₂ COU₁, in which V₂ is hydrogen or alkyl having 1 or 2 carbon atoms and U₁ is as defined above, or R₆ is N-alkyl-substituted or N,N-dialkyl-substituted carboxamido or sulfonamido, in which each alkyl moiety contains 1 to 10 carbon atoms and can be substituted further, or R₆ is substituted or unsubstituted alkylsulfone having 1 to 8 carbon atoms, substituted or unsubstituted phenylsulfone, substituted or unsubstituted phenoxy or substituted or unsubstituted phenylsulfonic acid ester, or is hydroxyl, cyano, nitro or halogen, R₇ is hydrogen, substituted or unsubstituted alkyl having 1 to 8 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety contains 1 to 8 carbon atoms and can be substituted, or R₇ is substituted or unsubstituted alkylsulfone having 1 to 6 carbon atoms, substituted or unsubstituted phenylsulfone or substituted or unsubstituted phenoxy, or is cyano, nitro or halogen, R₈ is hydrogen, alkyl or alkoxy having 1 to 4 carbon atoms, substituted or unsubstituted phenoxy or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms, or R₈ is alkylsulfone having 1 to 4 carbon atoms, substituted or unsubstituted phenylsulfonic acid ester, cyano, nitro, halogen, substituted or unsubstituted carbalkoxy having 1 to 16 carbon atoms, or --P(O)(OT¹)₂, in which T¹ is as defined above, R₉ is hydrogen, unsubstituted or halogen-substituted alkyl having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 to 16 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted, or R₉ is --NQ₁ COT₁, in which Q₁ and T₁ are as defined above, or R₉ is alkylsulfone having 1 to 6 carbon atoms, phenylsulfone, hydroxyl, cyano, nitro or halogen, R₁₀ is hydrogen, alkyl having 1 to 4 carbon atoms or carbalkoxy having 2 to 13 carbon atoms, X₂ is hydrogen, alkyl or alkoxy, each having 1 to 6 carbon atoms, or --NL₂ COM₂, in which L₂ is hydrogen or alkyl having 1 to 4 carbon atoms and M₂ is substituted or unsubstituted alkyl or alkoxy having 1 to 18 carbon atoms, or X₂ is alkylsulfonylamino having 1 to 18 carbon atoms, or hydroxyl, Y₂ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 12 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms, or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety contains 1 to 6 carbon atoms and can be substituted, or Y₂ is substituted or unsubstituted phenylsulfonylamino or --NE₂ COG₂, in which E₂ is hydrogen or unsubstituted or cyano-substituted alkyl having 1 to 8 carbon atoms and G₂ is alkyl having 1 to 8 carbon atoms or substituted or unsubstituted alkoxy having 1 to 4 carbon atoms, or Y₂ is --NHP(O)(OG²)₂, in which G² is alkyl having 1 to 6 carbon atoms, or Y₂ is halogen or hydroxyl, Z₂ is hydrogen, alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms or --NA₂ COD₂, in which A₂ is hydrogen or alkyl having 1 to 8 carbon atoms and D₂ is alkyl having 1 to 18 carbon atoms, or Z₂ is acyl having 2 to 7 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 19 carbon atoms, alkylsulfonylamino having 1 to 6 carbon atoms, halogen or the atoms which together with Y₂ form an unsubstituted or methyl-substituted 6-membered, saturated or unsaturated ring which can contain one or two hetero-atoms and W₂ is hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, or halogen.

Particularly suitable compounds of the formula (2) are those of the formula ##STR10## in which R₁₁ is hydrogen, alkyl having 1 to 12 carbon atoms which is substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 12 carbon atoms or is unsubstituted, alkoxy having 1 to 16 carbon atoms, a radical of the formula

    --O--(CH.sub.2).sub.m.sbsb.1 --OC.sub.2 H.sub.4 ].sub.n O--CH.sub.2).sub.m CH.sub.3,

in which m₁ is an integer from 2 to 16, n is 1 or 2 and m is an integer from 0 to 3, alkenyl having 2 to 4 carbon atoms, which is substituted by cyano and/or by carbalkoxy having 2 to 9 carbon atoms or is unsubstituted, aliphatic acyl having 2 or 3 carbon atoms, benzoyl which is substituted by chlorine, CO₂ B₁, --SO₂ B₁ or --COB₁, in which B₁ is alkyl having 1 to 8 carbon atoms, or is unsubstituted, or R₁₁ is carbalkoxy having 2 to 16 carbon atoms, a radical of the formula ##STR11## in which m₁ and n are as defined above, or --NV₃ COU₂, in which V₃ is hydrogen and U₂ is unsubstituted or methoxy- or hydroxyl-substituted alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 4 carbon atoms, or R₁₁ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 10 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₁ is alkylsulfone having 1 to 8 carbon atoms, unsubstituted or substituted phenylsulfone, unsubstituted or substituted phenoxy, unsubstituted or substituted phenylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R₁₂ is hydrogen, unsubstituted or halogen-substituted alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR12## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted by methoxy, or R₁₂ is alkylsulfone having 1 to 6 carbon atoms, phenylsulfone or phenoxy which is unsubstituted or substituted by alkyl having 1 to 8 carbon atoms, or is cyano, nitro or halogen, R₁₃ is hydrogen, unsubstituted or fluorine-substituted alkyl having 1 or 2 carbon atoms, unsubstituted or methoxy-substituted alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 to 13 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, or R₁₃ is --NQ₂ COT₂, in which Q₂ is hydrogen and T₂ is alkyl having 1 to 4 carbon atoms, or R₁₃ is methylsulfone, phenylsulfone, hydroxyl, cyano, nitro or halogen, X₃ is hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, or --NL₃ COM₃, in which L₃ is hydrogen or methyl and M₃ is alkyl which has 1 to 18 carbon atoms and is unsubstituted or substituted by halogen, by carbalkoxy having 2 to 5 carbon atoms, by substituted or unsubstituted phenyl or phenoxy or by alkoxy having 1 to 5 carbon atoms, or X₃ is alkylsulfonylamino having 1 to 12 carbon atoms or hydroxyl, Y₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 12 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted by carbalkoxy having 2 to 5 carbon atoms, by methoxy, by acetoxy, by hydroxyl, by nitro, by cyano, by phenyl or by tosyl, or Y₃ is pyrrolidinyl, piperidinyl, morpholinyl or phenylsulfonylamino which is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, or Y₃ is --NE₃ COG₃, in which E₃ is hydrogen or unsubstituted or cyano-substituted alkyl having 1 to 4 carbon atoms and G₃ is alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 4 carbon atoms or a radical of the formula --O--(CH.sub. 2)_(k) --OC₂ H₄)_(n) OCH₃ in which k is an integer from 2 to 5 and n is as defined above, or Y₃ is ##STR13## in which G³ is alkyl having 1 to 4 carbon atoms, or Y₃ is halogen or hydroxyl, Z₃ is hydrogen, alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms, a radical of the formula --O--(CH₂)_(k).sbsb.1 --O--(CH₂)_(m) --CH₃ in which k₁ is an integer from 2 to 6 and m is as defined above, or Z₃ is --NA₃ COD₃, in which A₃ is hydrogen or alkyl having 1 to 4 carbon atoms and D₃ is alkyl having 1 to 12 carbon atoms, or Z₃ is acyl having 2 to 5 carbon atoms, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR14## in which k and n are as defined above, methylsulfonylamino, halogen or the atoms which together with Y₃ form an unsubstituted or methyl-substituted 6-membered saturated or unsaturated ring which contains nitrogen or nitrogen and oxygen, W₃ is hydrogen, alkyl or alkoxy each having 1 or 2 carbon atoms, or halogen, and R₈ and R₁₀ are as defined above.

Further compounds which are preferred are those of the formula ##STR15## in which R₁₄ is hydrogen, alkyl which has 1 to 12 carbon atoms and is unsubstituted or substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 7 carbon atoms, alkoxy having 1 to 12 carbon atoms, a radical of the formula --O(CH₂)_(m).sbsb.2 --OC₂ H₄)_(n) O(CH₂)_(m) CH₃ in which m₂ is an integer from 2 to 12 and n and m are as defined above, or alkenyl which has 2 to 4 carbon atoms and is unsubstituted or substituted by cyano and/or by carbalkoxy having 2 to 7 carbon atoms, or R₁₄ is aliphatic acyl having 2 or 3 carbon atoms, or benzoyl which is unsubstituted or substituted by chlorine, --CO₂ B₂, --SO₂ B₂ or --COB₂, in which B₂ is alkyl having 1 to 4 carbon atoms, or R₁₄ is carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR16## in which m₃ is an integer from 2 to 8 and n is as defined above, or --NHCOU₃, in which U₃ is alkyl having 1 to 8 carbon atoms or alkenyl having 2 or 3 carbon atoms, or R₁₄ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₄ is alkylsulfone having 1 to 6 carbon atoms, unsubstituted or C₁₋₅ -alkyl-substituted or hydroxyl-substituted phenylsulfone or phenylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R₁₅ is hydrogen, unsubstituted or fluorine-substituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR17## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, or R₁₅ is alkylsulfone having 1 to 4 carbon atoms, or phenylsulfone, or R₁₅ is cyano, nitro or halogen, R₁₆ is hydrogen, methyl, methoxy or unsubstituted, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, or R₁₆ is alkylsulfone having 1 to 4 carbon atoms, phenylsulfonic acid ester, cyano, nitro, halogen, unsubstituted or methoxy-substituted carbalkoxy having 1 to 12 carbon atoms or --P(O)(OT¹)₂, in which T¹ is as defined above, R₁₇ is hydrogen, methyl, trifluoromethyl, or alkoxy having 1 to 4 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, or R₁₇ is --NHCOT₂, in which T₂ is as defined above, or R₁₇ is methylsulfone, phenylsulfone, hydroxyl, cyano, nitro or halogen, R₁₈ is hydrogen, methyl or carbalkoxy having 2 to 7 carbon atoms and X₃, Y₃, Z₃ and W₃ are as defined above.

Further useful compounds are those of the formula ##STR18## in which X₄ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NL₄ COM₄, in which L₄ is hydrogen or methyl and M₄ is alkyl having 1 to 13 carbon atoms, or alkoxy having 1 to 4 carbon atoms, which can both be substituted by fluorine, chlorine or carbalkoxy having 2 or 3 carbon atoms, or by phenyl or phenoxy or by (C_(m).sbsb.3 H_(2m).sbsb.3₊₁ --C₆ H₄ -- or (C_(m).sbsb.3 H_(2m).sbsb.3₊₁ --(--C₆ H₄ --O-- or by alkoxy having 1 to 5 carbon atoms, m₃ being as defined above, or X₄ is alkyl-sulfonylamino having 1 to 6 carbon atoms, or hydroxyl, Y₄ is hydrogen, alkyl having 1 or 2 carbon atoms, alkoxy having 1 to 8 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted by carbalkoxy having 2 to 5 carbon atoms, methoxy, acetoxy, hydroxyl, nitro, cyano or phenyl or Y₄ is pyrrolidinyl, piperidinyl or phenylsulfonylamino which can be substituted by alkyl having 1 to 4 carbon atoms, or Y₄ is --NE₃ CO--G₄, in which E₃ is as defined above and G₄ is alkyl having 1 to 8 carbon atoms, alkoxy having 1 or 2 carbon atoms, or a radical of the formula --O--CH₂ --CH₂ --OC₂ H₄ --OC₂ H₅ or --O--CH₂ --CH₂ --OC₂ H₄ --OCH₃, or Y₄ is ##STR19## in which G³ is as defined above, or Y₄ is halogen or hydroxyl, Z₄ is hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, --O(CH₂)_(k) --O(CH₂)_(m) --CH₃, in which k and m are as defined above, or --NA₄ COD₄, in which A₄ is hydrogen or methyl and D₄ is alkyl having 1 to 8 carbon atoms, or Z₄ is acetyl, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR20## in which k is as defined above, methylsulfonylamino, halogen or the atoms which together with Y₄ form ring systems such as ##STR21## W₄ is hydrogen, methyl, methoxy or halogen and R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ are as defined above.

Valuable compounds of the formula (5) are those of the formula ##STR22## in which R₁₉ is hydrogen, alkyl having 1 to 6 carbon atoms which can be substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 7 carbon atoms, alkoxy having 1 to 8 carbon atoms, a radical of the formula --O--CH₂)_(m).sbsb.3 OC₂ H₄ --OCH₃ or --O--CH₂)_(m).sbsb.3 OC₂ H₄ --OC₂ H₅, in which m₃ is as defined above, vinyl which can be substituted by cyano and/or by carbalkoxy having 2 to 7 carbon atoms, acetyl, benzoyl which can be substituted in the para-position by chlorine, --CO₂ B₂, --SO₂ B₂ -- or --COB₂, in which B₂ is as defined above, carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR23## in which m₃ is as defined above, or --NHCOU₄, in which U₄ is alkyl having 1 to 4 carbon atoms or alkenyl having 2 or 3 carbon atoms, or R₁₉ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₉ is alkyl-sulfone having 1 to 6 carbon atoms or phenylsulfone or phenylsulfonic acid ester, which two radicals can be substituted in the para-position by alkyl having 1 to 5 carbon atoms or hydroxyl, or R₁₉ is hydroxyl, cyano, nitro, chlorine or bromine, R₂₀ is hydrogen, methyl, trifluoromethyl, methoxy, ethoxy, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR24## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, or R₂₀ is alkylsulfone having 1 to 4 carbon atoms or phenylsulfone, or R₂₀ is cyano, nitro, chlorine or bromine, R₂₁ is hydrogen, methyl, methoxy, or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 or 2 carbon atoms, or R₂₁ is alkylsulfone having 1 to 4 carbon atoms, cyano, nitro, bromine, chlorine or unsubstituted or methoxy-substituted carbalkoxy having 2 to 7 carbon atoms, or R₂₁ is --P(O)(OC₂ H₅)₂, R₂₂ is hydrogen, methyl, trifluoromethyl, unsubstituted or methoxy-substituted alkoxy having 1 or 2 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be substituted by methoxy, or R₂₂ is --NHCOT₂, in which T₂ is as defined above, or R₂₂ is methylsulfone, phenylsulfone, hydroxyl, cyano, chlorine or bromine, R₂₃ is hydrogen, methyl or carbalkoxy having 2 or 3 carbon atoms, X₅ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NL₅ --COM₅, in which L₅ is hydrogen and M₅ is alkyl having 1 to 8 carbon atoms, or alkoxy having 1 or 2 carbon atoms, which radicals can be substituted by fluorine, chlorine, carbalkoxy having 2 or 3 carbon atoms, phenyl, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --, phenoxy, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O-- or alkoxy having 1 to 5 carbon atoms, m₃ being as defined above, or X₅ is alkylsulfonylamino having 1 to 6 carbon atoms, or hydroxyl, W₅ is hydrogen, methyl, methoxy or chlorine and Y₄ and Z₄ are as defined above.

Particularly useful compounds are those of the formula ##STR25## in which R₂₄ is hydrogen or alkyl having 1 to 4 carbon atoms, which can be substituted by carbalkoxy having 2 to 7 carbon atoms, or R₂₄ is alkoxy having 1 to 4 carbon atoms, a radical of the formula --O--(CH₂)_(k) --OC₂ H₄ --OCH₃ or --O--(CH₂)_(k) --OC₂ H₄ --OC₂ H₅, in which k is as defined above, carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR26## in which m₃ is as defined above, --NHCOU₄, in which U₄ is as defined above, carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be substituted by methoxy, or R₂₄ is alkyl-sulfone having 1 to 6 carbon atoms or is phenylsulfone or phenylsulfonic acid ester, each of which two radicals can be substituted in the para-position by alkyl having 1 to 5 carbon atoms or hydroxyl, or R₂₄ is hydroxyl, nitro, chlorine or bromine, R₂₅ is hydrogen, methyl, methoxy, ethoxy, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR27## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be substituted by methoxy, or R₂₅ is alkylsulfone having 1 to 4 carbon atoms or phenoxy which can be substituted in the para-position by alkyl having 1 to 5 carbon atoms, or R₂₅ is cyano, nitro, chlorine or bromine, R₂₆ is hydrogen, cyano, chlorine or bromine, R₂₇ is hydrogen or alkoxy having 1 or 2 carbon atoms, or R₂₇ is carbalkoxy having 2 to 9 carbon atoms, --NHCOT₂, in which T₂ is as defined above, hydroxyl or chlorine, R₂₈ is hydrogen or carbalkoxy having 2 or 3 carbon atoms, X₆ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NHCOM₆, in which M₆ is alkyl having 1 to 4 carbon atoms which is optionally substituted by alkoxy having 1 to 5 carbon atoms, by phenoxy or by para-(C_(k) H_(2k+1))--C₆ H₄ --O--, k being as defined above, or X₆ is hydroxyl, Y₅ is hydrogen, alkoxy having 1 to 4 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by carbalkoxy having 2 or 2 carbon atoms, methoxy, acetoxy, hydroxyl, nitro, cyano or phenyl, or Y₅ is --NE₃ COG₄, in which E₃ and G₄ are as defined above, or Y₅ is hydroxyl, Z₅ is hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, acetyl, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR28## in which k is as defined above, --NA₄ COD₄, in which A₄ and D₄ are as defined above, or chlorine, and W₅ is as defined above.

Particularly suitable compounds are those of the formula ##STR29## in which R₂₉ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or a radical of the formula ##STR30## in which m₃ is as defined above, R₃₀ is hydrogen, methyl, methoxy, cyano, chlorine or bromine, R₃₁ is hydrogen or bromine, R₃₂ is hydrogen or chlorine, R₃₃ is hydrogen or carbomethoxy, X₇ is ##STR31## in which M₇ is alkyl having 1 to 4 carbon atoms, or X₇ is hydroxyl, Y₆ is hydrogen, N-alkyl-substituted amino, in which the alkyl moiety has 1 or 2 carbon atoms and can be cyano-substituted, or --NE₃ COG₄, in which E₃ and G₄ are as defined above, Z₆ is hydrogen or alkoxy having 1 to 4 carbon atoms and W₆ is hydrogen or methyl.

Particularly valuable compounds are those of the formulae ##STR32##

The compounds of the formulae (7) to (11) are particularly suitable for use as yellow dyes in photographic layers of silver dye bleach materials.

Other preferred compounds are those of the formula ##STR33## in which R₃₄ is hydrogen or alkyl having 1 or 2 carbon atoms, which can be substituted by carbalkoxy having 2 or 3 carbon atoms, or is carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR34## or vinyl which can be substituted by cyano and/or carbalkoxy having 2 to 5 carbon atoms, or R₃₄ is N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 3 carbon atoms and can be methoxy-substituted, alkylsulfone having 1 to 6 carbon atoms, phenylsulfonic acid ester, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O--SO₂ --, in which m₃ is as defined above, cyano, nitro, chlorine or bromine, R₃₅ is hydrogen, trifluoromethyl, carbalkoxy having 2 or 3 carbon atoms, alkylsulfone having 1 to 4 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, cyano, nitro, chlorine or bromine, R₃₆ is hydrogen, methylsulfone, N,N-diethylsulfonamide, cyano, nitro, chlorine or bromine, R₃₇ is hydrogen, methyl, carbalkoxy having 2 to 7 carbon atoms, N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, cyano or chlorine, R.sub. 38 is hydrogen or methyl, X₈ is hydrogen, methyl or --NHCOM₇, in which M₇ is alkyl having 1 to 8 carbon atoms which is unsubstituted or substituted by carbalkoxy having 2 or 3 carbon atoms, fluorine, chlorine, phenyl, phenoxy, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊)--C₆ H₄ -- or para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ O--, or X₈ is alkylsulfonylamino having 1 to 6 carbon atoms, or hydroxyl, Y₇ is alkyl having 1 or 2 carbon atoms, alkoxy having 1 to 8 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms, or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, carbomethoxy, acetoxy, cyano, hydroxyl or phenyl, or Y₇ is --NHCOG₅, in which G₅ is alkyl having 1 to 4 carbon atoms, and Z₇ is hydrogen, alkoxy having 1 or 2 carbon atoms, a radical of the formula --OCH₂ CH₂ --O(CH₂)_(m) --CH₃, in which m is as defined above, --NHCOD₄, in which D₄ is as defined above, or chlorine.

Further useful compounds are those of the formula ##STR35## in which R₃₉ is hydrogen or alkyl having 1 or 2 carbon atoms, which can be substituted by carbalkoxy having 2 or 3 carbon atoms, or R₃₉ is carbalkoxy having 2 or 3 carbon atoms, alkylsulfone having 1 to 6 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 3 carbon atoms and can be methoxy-substituted, cyano, nitro, chlorine or bromine, R₄₀ is hydrogen, alkylsulfone having 1 to 4 carbon atoms, N,N-dimethylsulfonamide or N,N-diethylsulfonamide, cyano or nitro, R₄₁ is hydrogen, methylsulfone, cyano or nitro, R₄₂ is hydrogen or cyano, X₉ is methyl or ##STR36## in which M₈ is alkyl having 1 to 4 carbon atoms, or X₉ is hydroxyl, Y₈ is alkoxy having 1 to 8 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, acetoxy or cyano, and Z₈ is hydrogen, alkoxy having 1 or 2 carbon atoms, a radical of the formula --OCH₂ CH₂ --O(CH₂)_(m) --CH₃, in which m is as defined above, or --NHCOD₄, in which D₄ is as defined above.

Particularly valuable compounds of the formula (13) are the compounds of the formulae ##STR37##

The compounds of the formulae (14) to (17) are particularly useful as magenta dyes in photographic layers of silver dye bleach materials.

Further preferred compounds are those of the formula ##STR38## in which R₄₃ is vinyl which can be substituted by cyano and/or carbalkoxy having 2 to 7 carbon atoms, or R₄₃ is carbalkoxy having 2 or 3 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be methoxy-, amino- or hydroxyl-substituted, alkylsulfone having 1 to 6 carbon atoms, phenylsulfonic acid ester, para-(C_(m).sbsb.3 H_(2m).sbsb.3+1)--C₆ H₄ --O--SO₂ --, in which m₃ is as defined above, cyano or nitro, R₄₄ is N,N-dimethylsulfonamido or N,N-diethylsulfonamido, cyano, nitro, chlorine or bromine, methylsulfone or trifluoromethyl, R₄₅ is hydrogen, cyano, nitro, chlorine or bromine, R₄₆ is hydrogen or carbalkoxy having 2 to 6 carbon atoms, X₁₀ is methyl, ##STR39## in which M₅ is as defined above, or alkylsulfonamido having 1 to 6 carbon atoms, Y₉ is unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, acetoxy, cyano, hydroxyl, or phenyl, and Z₉ is hydrogen, methoxy, --OCH₂ --CH₂ --OC₂ H₅ or --OCH₂ CH₂ --OCH₃.

Amongst these, particularly useful compounds are those of the formula ##STR40## in which R₄₇ is vinyl which can be substituted by cyano and/or carbalkoxy having 2 or 3 carbon atoms, or R₄₇ is N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, cyano or nitro, R₄₈ is cyano or trifluoromethyl or nitro, X₁₁ is ##STR41## in which M₈ is as defined above, and Y₁₀ is dimethylamino or diethylamino.

Valuable compounds include those of the formulae ##STR42##

The compounds of the formulae (20) and (21) are particularly useful as cyan dyes in photographic layers of silver dye bleach materials.

The compounds of the formula (1) to (21), dissolved in oil, exhibit a plurality of advantages.

Thus, they are distinguished by high stability of their emulsions. The tendency to micelle formation is entirely absent, and accordingly there is no adverse influence on the colour density of the photographic images.

The oil serves not only as a solvent for the dyes, but can also be a plasticiser for the gelatin. This substantially prevents the possible detachment, which can in particular occur under moist conditions of the photographic layers from the base.

As a result of the good solubility of the dyes in oil, a large amount of dye can be accommodated in one small drop of oil. Accordingly, photographic materials can be cast with very thin layers. This has a beneficial influence on the sharpness of the image.

Because of their insolubility in water, the dyes can be isolated in a very pure form. They are prepared by conventional methods, for example by diazotising an amine of the formula ##STR43## in which R₁, R₂, R₃, R₄ and R₅ are as defined above, in a conventional manner, in the presence or absence of an organic solvent, and coupling the product with a coupling component of the formula ##STR44## in which X₁, Y₁, Z₁ and W₁ are as defined above, in the presence or absence of an organic solvent and in the presence or absence of a base.

When preparing an azo dye of the formula (1), in which the substituent R₂ and R₃ is cyano, it is advantageous to introduce the cyano group by an exchange reaction with the corresponding halogen-containing compound.

If R₂ and R₃ in formula (1) are alkylsulfone, it is also possible to prepare the corresponding azo compounds from the halogen-containing compound by reacting the latter with a suitable sulfinate, in the presence or absence of Cu⁺.

Examples of diazo components of the formula (22) are 4-ethylaniline, 4-dodecylaniline, 2-, 3- or 4-toluidine, 2-, 3- or 4-anisidine, 4-phenetidine, 4-butylaniline, 2-, 3- or 4-fluoroaniline, 2-, 3- or 4-chloroaniline, 2-, 3- or 4-bromoaniline, 2-, 3- or 4-trifluoromethylaniline, methyl anthranilate, ethyl anthranilate, 2'-methoxyethyl anthranilate, ethyl 4-aminobenzoate or 2'-ethylhexyl 4-aminobenzoate, 3',6'-dioxaheptyl 4-aminobenzoate, methyl 3-aminobenzoate, phenyl 4-aminobenzoate, anthranilic acid N,N-bis-(2'-methoxyethyl)-amide, 4'-aminobenzanilide, 4-amino-diphenyl ether, 4-aminobenzaldehyde, 2-, 3- or 4-amino-acetophenone, 4-amino-benzophenone, 4-amino-4'-hydroxydiphenylsulfone, 2-, 3- or 4-aminophenyl methyl sulfone, diethyl 2-aminophenylphosphonate, 2-, 3- or 4-methylmercaptoaniline, 4-phenylmercaptoaniline, 4-aminophenyl hexyl sulfone, 4-aminophenyl isobutyl sulfone, isobutyl p-aminophenylacetate, 4-aminobenzenesulfonic acid N-dodecylamide, 4-aminophenyl 3',6'-dioxaheptyl ether, 4-amino-4'-nitrobenzophenone, 4-isobutoxyaniline, 4-butoxyaniline, 4-aminobenzenesulfonic acid N,N-diisopropylamide, 4-aminobenzenesulfonic acid N,N-bis-(2'-methoxyethyl)-amide, 4-aminobenzenesulfonic acid 3'-methoxypropylamide, phenyl 4-aminobenzenesulfonate, 4'-t-pentyl-phenyl 4-aminobenzenesulfonate, 4-aminobenzenesulfonic acid N,N-diethylamide, 3-benzoylamino-4-nitroaniline, isobutyl 4-aminobenzoate, 4-benzoylamino-3-nitroaniline, dibutyl 4-aminophthalate, methyl 4-aminocinnamate, ethyl 4-aminocinnamate, bis-(2'-ethylhexyl) 4-aminophthalate, 3-methyl-4-nitroaniline, 4-butylaniline, 4-cyclopropylaniline, 3-fluoro-4-nitroaniline, methyl 3 -amino-4-chlorobenzoate, ethyl 3-amino-4-chlorobenzoate, 2-methyl-5-methylmercapto-4-nitroaniline, 3-methoxy-4-nitroaniline, 2-methoxy-5-chloroaniline, 3-methylmercapto-4-nitroaniline, 4-methyl-3-chloroaniline, 4-methylmercapto-3-nitroaniline, 4-amino-3-chlorophenyl methyl sulfone, ethyl 5-amino-4-bromo-2-carbamoyl-benzoate, 4-amino-5-bromobenzene-1,3-disulfonic acid bis-N,N-diethylamide, 4-amino-3,5-dibromobenzenesulfonic acid N,N-(bis-2'-methoxyethyl)-amide, 3,4-bis-(2'-methoxyethoxy)-aniline, 2,4-bis-isobutylsulfonyl-aniline, 2,5-dibromo-4-butoxyaniline, 4-amino-3,5-dibromophenyl isopentyl ether, 4-isobutoxy-2-methoxyaniline, 3-bromo-4-butoxy-aniline, dimethyl 5-amino-2,4,6-tribromoisophthalate, ethyl 3-amino-2,4,6-tribromobenzoate, 2-amino-5-nitrobenzoic acid N-piperidide, 2-amino-5-nitrobenzoic acid N-pyrrolidide, 2-amino-5-nitrobenzoic acid N-morpholide, 4-amino-3-bromo-5-methyl-benzenesulfonic acid N-morpholide, 3-amino-4-chlorobenzotrifluoride, 5-amino-2-chlorobenzotrifluoride, ethyl 4-amino-3-methyl-benzoate, ethyl 3-amino-4-methyl-benzoate, 4-bromo-2,6-dimethylaniline, 4-bromo-2-methylaniline, 4-bromo-3-methylaniline, 2-bromo-4-methylaniline, 5-chloro-2,4-dimethoxyaniline, 4-chloro-2-methylaniline, 2-chloro-6-methylaniline, 2-methoxy-5-methylaniline, 4-methoxy-2-methylaniline, 2-methoxy-5-nitroaniline, 4-methoxy-2-nitroaniline, 2-methyl-3-, -4-, -5- or -6-nitroaniline, 4-methyl-2- or -3-nitroaniline, 2,3,4-, 2,4,5-, 2,4,6- or 3,4,5-trichloroaniline, 3,4,5-trimethoxyaniline, 2,4,6-trimethylaniline, 3,5-bis-trifluoromethyl-aniline, 2,6-difluoroaniline, 4-aminomethacrylanilide, 2'-, 3'- or 4'-amino-phenyl methanesulfonate, 2'-, 3'- or 4'-aminophenyl toluenesulphonate, 4-amino-3,5-dibromo-acetanilide, 4-chloro-3-nitroaniline, 3-chloro-6-nitroaniline, N,N-bis-(2'-methoxyethyl)-anthranilamide, 2-acetamido-5-aminobenzonitrile, 3-amino-4-methylmercapto-benzenesulfonic acid N,N-bis-(2' -methoxyethyl)-amide, 2-, 3- or 4-aminobenzonitrile, 2-amino-4-, -5- or -6-chlorobenzonitrile, 2-amino-3,5-dibromo-benzonitrile, 2-chloro-4-methoxyaniline, 2-chloro-5-methoxyaniline, 4-[4'-terpentylphenoxy]-aniline, 2,5-dimethoxy-4-nitroaniline, 4-chloro-3-aminobenzoic acid N-hexylamide, 4-(2'-methoxyethoxy)-anilide, 2-methoxy-5-(t-butyl)-aniline, 3-nitro-4-methoxy-aniline, 4-methoxy-2-nitro-aniline, 5-amino-2-methoxy-butyraniline, 3-methoxy-4-nitro-aniline, 3-amino-4-methoxy-propionanilide, 2'-ethyl-hexyl 3-amino-4-methylsulfonyl-benzoate, ethyl 4-amino-3,5-dibromobenzoate, 4-amino-3,5-dibromo-toluidine, 4-amino-3,5-dibromo-chlorobenzene, 4-amino-3,5-dibromo-ethylbenzene, 4-amino-3,5-dibromo-fluorobenzene, 2,4,6-tribromoaniline, 4-amino-3,5-dibromo-phenetidine, methyl 3-[4'-amino-3',5'-dibromophenyl]-propionate, ethyl 3-[4'-amino-3',5'-dibromophenyl]-propionate, 2'-methyl-pentyl-3-[4'-amino-3',5'-dibromophenyl]-propionate, 2-amino-3-bromo-5-nitro-benzotrifluoride, 2-amino-3-bromo-5-nitrophenyl methyl sulfone, 2-amino-3-bromo-5 -nitro-benzonitrile, 3-[4'-amino-3',5'-dibromophenyl]-propionitrile, 2'-ethylhexyl 3-amino-4-methylsulfonyl-benzoate, 3,4-bis-(2'-methoxyethoxy)-aniline, 5-acetamido-2-methoxyaniline, 4-amino-3,5-dibromophenyl methyl sulfone, 4-amino-3,5-dibromo-benzonitrile, 2-amino-4-chlorobenzenesulfonic acid N-isobutylamide, ethyl 4-amino-2-hydroxybenzoate, dimethyl 2-aminoterephthalate, diethyl 5-amino-isophthalate, 4-amino-3,5-dibromobenzenesulfonamide, dimethyl 4-amino-isophthalate, ethyl 4-amino-3-methoxy-benzoate, ethyl 3-amino-4-methoxy-benzoate, ethyl 4-amino-3-nitro-benzoate, ethyl 5-amino-2-hydroxybenzoate, 4-amino-3-bromophenyl hexyl sulfone, 4-hexylmercaptoaniline, 4-dodecyloxyaniline, 4-amino-3-methylphenyl octyl ether, ethyl 4-amino-cinnamate, 4-amino-cinnamonitrile, 2-nitro-3,5-dimethylaniline, 2'-methylpentyl 4-amino-hydrocinnamate, ethyl 3-amino-4-cyanobenzoate or 3',6'-dioxaheptyl 3-amino-4-cyanobenzoate, dodecyl 4-aminophenylacetate, isobutyl 4-aminophenylacetate, 4-aminobenzenesulphonic acid N-dodecylamide or N,N-bis-(2'-hydroxypropyl)-amide, 4-amino-3,5-dibromobenzotrifluoride, 4-amino-3,5-dibromobenzenesulfonic acid N-(3'-diethylamino-2'-methyl-butyl)-amide or N,N'-diethylamide, 3',6'-dioxaoctyl 4-amino-3,5-dibromobenzoate, 4-amino-3,5-dibromobenzaldehyde, 4-aminobenzoic acid N-(3'-methoxypropyl)-amide, 3',6'-dioxaheptyl 5-amino-4-bromo-2-cyanobenzoate, 3-[4'-aminophenyl]-2-chloroprioponitrile, 2',4'-di-tert.pentyl-phenyl sulfanilate, methyl 4-amino-hydrocinnamate, ethyl 4-amino-hydrocinnamate, 3,4-dimethoxyaniline, 3,4-diethoxyaniline, ethyl 4-amino-3,5-dibromophenylacetate, 4-amino-3,5-dibromohydrocinnamonitrile, 4-amino-3,5-dibromoacetophenone, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylaniline, 2-, 3- or 4-nitroaniline, 4-aminobenzene-1,3-disulfonic acid bis-N,N'-diethylamide, 2,6-diethylaniline, 4-dodecylaniline, 4-butylaniline, 4-t.-butylaniline, 2,4-, 2,5-, 3,5- or 3,4-dimethoxyaniline, 2,4-bis-(4'-tert.-pentylphenoxy)-aniline, 4-(2'-ethyl-hexyloxy)-aniline, 2,4-, 2,5- or 2,6-dibromoaniline, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichloroaniline, methyl, ethyl, butyl, benzyl, pentyl, 2'-methoxyethyl or 2'-ethoxyethyl 3-aminobenzoate, 3-aminobenzoic acid butylamide, 3-methoxypropylamide, diethylamide or pyrrolidide, 4-aminophthalic acid N-3'-methoxypropyl-imide, 3- or 4-aminoacetanilide, ethyl 3-aminobenzoate, isobutyl 3-aminobenzoate, ethyl 2-amino-5-nitrobenzoate, 3',6'-dioxaoctyl 2-amino-5-nitrobenzoate, 4-butyl-2,6-dibromoaniline, methyl 3-amino-2,4-dibromo-6-nitro-benzoate, 2-chloro-4,6-dinitroaniline, 2-bromo-4,6-dinitroaniline, isopentyl 4-amino-3,5-dibromobenzophenone-4'-carboxylate, 2,6-dibromo-4-nitroaniline, 4-amino-2-ethoxy-3,5-dibromo-toluene, ethyl 4-amino-3-bromo-5-nitrobenzoate, 2-bromo-6-methyl-4-nitroaniline, 4-amino-3,5-dibromophenyl hexyl sulfone, 4-amino-3,5-dibromobenzenesulfonic acid N-(3'-methoxypropyl)-amide, 4-amino-3,5-dibromobenzenesulfonic acid N-(3'-butoxypropyl)-amide, 2-bromo-4,6-diisobutylsulfonyl-aniline, 4-amino-5-bromobenzene-1,3-disulfonic acid bis-N,N'-diethylamide, 2 -amino-3-bromo-5-nitrobenzenesulfonic acid 3'-methoxypropylamide, 4-amino-3,5-dibromo-benzotrifluoride, 3-amino-2,5-dibromo-6-nitrobenzotrifluoride, 4-amino-3-bromo-4'-chloro-5-nitrobenzophenone, methyl 4-amino-3,5-dibromocinnamate, ethyl 4-amino-3,5-dibromocinnamate, 3-(4'-amino-3',5'-dibromophenyl)-2,3-dicyano-acrylonitrile, ethyl 3-(4'-amino-3',5'-dibromophenyl)-2-cyanoacrylate, butyl 3-(4'-amino-3',5'-dibromophenyl)-2-cyanoacrylate, 3-(4'-amino-3',5'-dibromophenyl)-2-cyanoacrylonitrile, ethyl 4-amino-3-bromo-5-nitrobenzoate, 2-amino-3-bromo-5-nitro-benzonitrile, 2,4- or 2,6-dinitroaniline, 4-amino-3,5-dibromoacetophenone, 2,4- or 2,5-dicyanoaniline, 5-amino-4-bromo-2-nitrophenyl methyl sulfone, 2-amino-3-bromo-5-nitrobenzenesulfonic acid N,N-dimethylamide, 2,6-dicyano-4-nitroaniline, 2,6-dicyano-3,5-dimethylaniline, 2,6-dibromo-3-methyl-4-nitroaniline, isobutyl 3-amino-2,4-dibromo-6-nitro-benzoate, methyl 3-amino-2,4-dibromo-6-nitro-benzoate, 3-amino-2,4-dibromo-6-nitrophenyl isobutyl sulfone and 4-amino-3,5-dibromo-2-nitrophenyl isobutyl sulfone.

Suitable coupling components of the formula (23) include the following: ##STR45##

The dyes of the formula (1) can be used for various purposes, but especially in photographic materials, and especially advantageously as image dyes for the silver dye bleach process. Accordingly, very useful photographic materials, especially silver dye bleach materials, which comprise at least one layer, containing a dye of the formula (1), on a base can be prepared in a conventional manner known per se.

A transparent, metallically reflecting or, preferably, opaque white material can be used as the base for the silver halide emulsion layer; preferably, the base should not be capable of absorbing liquid from the baths.

The base can consist, for example, of unpigmented or pigmented cellulose triacetate or polyester. Should it consist of paper fibres, it must be lacquered or polyethylene-coated, on both sides. On at least one side of this base are the light-sensitive layers, preferably in the conventional arrangement, i.e. a red-sensitised silver halide emulsion layer, containing a cyan azo dye, as the lowest layer, on top of this a green-sensitised silver halide emulsion layer containing a magenta azo dye, and, as the uppermost layer, a blue-sensitive silver halide emulsion layer containing a yellow azo dye. The material can also contain subbing layers, intermediate layers, filter layers and protective layers, but the total thickness of the layers should as a rule not exceed 20μ.

The dyes according to the invention are lipophilic and are in general incorporated into the gelatins as solutions in high-boiling solvents. In most cases it suffices to add the dyes employed as a solution in such a solvent, with or without the addition of a volatile auxiliary solvent, to an aqueous gelatin solution at normal or slightly elevated temperature, with efficient stirring. The mixture is then brought together with a gelatin which contains silver halide and/or other materials for producing photographic images, cast on a base in a conventional manner to form a layer, and dried if appropriate.

Dyes of the formula (1), dissolved in organic solvents, can also be added direct to a gelatin which contains silver halide and/or other materials for producing photographic images. Thus, for example, it is possible to add the dye solution only immediately prior to casting.

Instead of simple stirring, the conventional methods of dispersing by means of kneading forces and/or shearing forces or ultrasonics can also be employed.

The dyes of formula (1) can also be incorporated into the coating solution according to Swiss Patent Application 4503/79-2 without applying shearing forces.

It is also possible to add the dye in a solid form, namely as a fine suspension, instead of as a solution. Furthermore, it is possible to incorporate the dyes into the gelatin in the presence of high-molecular polymers; latices are particularly useful for this application.

The casting solution can also contain other additives, such as hardeners, complexing agents and wetting agents, as well as sensitisers and stabilisers for the silver halide.

The dyes of the formula (1) do not undergo any chemical reactions with the light-sensitive materials. They are very diffusion-resistant, because they form stable, organic solutions. They are insensitive to calcium ions and easily dischargeable to white.

On addition to the casting solutions, the dyes produce neither an increase in viscosity nor a significant change in viscosity when the casting mixture is left to stand.

The spectral absorptions in gelatin are such that the dyes of the formula (1) can, if appropriate structures are chosen, be combined to form a dye tripack, composed of one yellow dye, one magneta dye and one cyan dye, the tripack showing grey shades, appearing neutral to the eye, over the entire density range.

The photographic silver dye bleach material produced with dyes of the formula (1) is in particular distinguished by brilliant colours, good colour reproduction and excellent light-fastness. An important characteristic of a good colour-copying material is excellent tone rendition and balanced colour gradations in all density ranges. The control of the colour equilibrium, in particular, repeatedly presents difficulties, since different bleaching characteristics of the azo dyes cannot always be compensated by the conventional methods of building up the material, such as balancing the sensitivity and contrast of the silver emulsions employed. This in many cases restricts the choice of the image dyes, and in particular also the choice of processing components in the bleaching bath.

In general, the exposed silver dye bleach materials are processed in four successive steps:

1. silver development

2. dye bleaching

3. silver bleaching

4. fixing

In the first step, the latent silver image formed on exposure is developed. In the second step, the image dye allotted to the silver is bleached, in accordance with the existing image-wise distribution of the silver. The third step is necessary in order to re-oxidise the excess image silver still present after dye bleaching. In the fourth step, the silver, which is now entirely present in the form of halides, is removed by dissolving out with a complexing agent, especially a salt of thiosulfuric acid, in order to make the finished image insensitive to additional exposure and to free the pure colour image from cloudiness.

The second process step, namely dye bleaching, is carried out, in the conventional known processes, in a strongly acid medium, a catalyst being added to accelerate the dye bleaching. The bleaching baths additionally contain a silver complexing agent or ligand. Both the constituents, namely catalyst and ligand, are necessary in order to transmit the reducing action of the metallic, non-diffusible image silver to the equally non-diffusible dye. The reduced form of the catalyst, which is formed by reduction at the image silver, here serves as an intermediate carrier, which, after travelling a certain diffusion distance, irreversibly reduces, and thereby bleaches, the dye, and is at the same time itself re-oxidised to the original form.

The ability of the reduced stage of the bleaching catalyst to diffuse freely between the image silver and the dye to be bleached makes it possible spatially to separate the silver and the image dye to a certain degree, i.e. the bleachable dye and the corresponding silver halide emulsion need not be present in the same layer but can be in adjacent layers, or need only partially be present in the same layer. Such silver dye bleach materials are described, for example, in German Pat. Nos. 2,036,918, 2,132,835 and 2,132,836.

A simplification of the processing method, in which the dye bleaching and silver bleaching are combined in a single process step, has been described in German Pat. No. 2,488,433.

The combined dye bleach and silver bleach baths (i.e. the formulations) for processing the exposed silver dye bleach material contain components (a) to (e) below, with or without component (f):

(a) strong acid

(b) water-soluble iodide

(c) water-soluble oxidising agent

(d) antioxidant

(e) bleaching catalyst

(f) bleaching accelerator

The amount of the bleaching catalysts which are employed in the--preferably aqueous--processing baths can vary within wide limits and is about 0.05 to 10 g/l of bleaching bath.

The temperature of the bleaching bath is in general between 20° and 90° C., preferably between 20° and 60° C.; of course, the requisite processing time is less at a higher temperature than at a lower temperature. The bleaching baths are stable within the stated temperature range. In general, the aqueous bleaching formulations required for the processing operation are employed in the form of dilute aqueous solutions, containing the stated components. Other methods, for example use of the formulation in paste form, are however also conceivable.

The stated temperature range also applies to the other processing steps. The aqueous bleaching formulation according to the present invention can be prepared, for example, from liquid, in particular aqueous, concentrates of some or all components ((a) to (f)). It is advantageous to use, for example, two liquid concentrates, of which one contains the strong acid (a) and the oxidising agent (c) and the other contains the remaining components (b), (d) and (e), with or without (f); in the latter concentrate, an additional solvent, such as ethyl alcohol, propyl alcohol, benzyl alcohol, ethylene glycol methyl ether or ethylene glycol ethyl ether, can be added to improve the solubility, especially of component (e). The aqueous bleaching formulations used as a rule contain components

(a) strong acid: 10 to 200 g/l;

(b) water-soluble iodide: 2 to 50 g/l, preferably 5 to 25 g/l;

(c) water-soluble oxidising agent: 1 to 30 g/l;

(d) antioxidant: 0.5 to 10 g/l;

(e) bleaching catalysts: 0.05 to 10 g/l, with or without

(f) bleaching accelerator: 1 to 20 g/l.

Strong acids (component (a)) which can be present in the combined dye bleaching and silver bleaching baths are alkylsulfonic acids or arylsulfonic acids, and especially p-toluenesulfonic acid, as well as sulfuric acid, sulfamic acid or trichloroacetic acid. Mixtures of these acids can also be employed. The pH value of the bleaching bath is in particular not greater than 2 and preferably not greater than 1.

The water-soluble iodides(component (b)) are as a rule alkali metal iodides, especially sodium iodide and potassium iodide.

The oxidising agents (c) employed are advantageously water-soluble aromatic mononitro and dinitro compounds and anthraquinonesulfonic acid derivatives. The use of such oxidising agents serves to influence the colour equilibrium and the contrast of the images produced by the dye bleach process and is known from German Pat. No. 735,672, British Pat. Nos. 539,190 and 539,509 and Japanese Patent Publication 22673/69.

The mononitro and dinitro compounds are preferably mononitrobenzenesulfonic acids or dinitrobenzenesulfonic acids, for example those of the formula ##STR46## in which n is 1 or 2 and R and R' are hydrogen, lower alkyl having 1 to 4 carbon atoms, hydroxyl, alkoxy, amino or halogen (chlorine or bromine). The sulfonic acids can be added as readily soluble salts. Examples of suitable salts are the sodium or potassium salts of the following acids: o-nitrobenzenesulfonic acid, m-nitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 3,5-dinitrobenzenesulfonic acid, 3-nitro-4-chlorobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, 4-methyl-3,5-dinitrobenzenesulfonic acid, 3-chloro-2,5-dinitrobenzenesulfonic acid, 2-amino-4-nitrobenzenesulfonic acid, 2-amino-4-nitro-5-methoxybenzenesulfonic acid and 4-nitrophenol-2-sulfonic acid.

The compounds constituting component (c) serve not only as silver bleaching agents but also to produce a flatter gradation.

The antioxidants (anti-corrosion agents (d)) used are advantageously reductones or water-soluble mercapto compounds. Suitable reductones are, in particular, aci-reductones which have a 3-carbonyl-1,2-diol grouping, such as reductone, triose-reductone or, preferably, ascorbic acid. Examples of suitable mercapto compounds include thioglycerol, but especially the compounds of the formula

    HS-C.sub.q H.sub.2.sbsb.q -B                               (25)

or preferably

    HS-(CH.sub.2).sub.m -COOH                                  (26)

in which q is an integer from 2 to 12, B is a sulfonic acid group or carboxylic acid group and m is 3 or 4. Mercapto compounds which can be used as antioxidants are described in German Pat. No. 2,258,076 and German Pat. No. 2,423,814. Other suitable antioxidants are adducts of alkali metal bisulfites, alkaline earth metal bisulfites or ammonium bisulfites with organic carbonyl compounds, preferably adducts of alkali metal bisulfites or ammonium bisulfites with monoaldehydes having 1 to 4 carbon atoms or dialdehydes having 2 to 5 carbon atoms (German Pat. No. 2,737,142).

Examples include the formaldehyde-bisulfite adduct, which is particularly preferred, and also the corresponding adducts of acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, glyoxal, malonodialdehyde or glutarodialdehyde. In some cases, the tertiary water-soluble phosphines referred to later as bleaching accelerators can at the same time serve as antioxidants.

Examples of suitable bleaching accelerators (f) are quaternary ammonium salts, such as are known from German Offenlegungsschriften Nos. 2,139,401 and 2,716,136. Preferably, they are quaternary, substituted or unsubstituted piperidine, piperazine, pyrazine, quinoline or pyridine compounds, the last-mentioned being preferred. Tetralkylammonium compounds (alkyl having 1 to 4 carbon atoms) and alkylenediammonium compounds (alkylene having 2 to 6 carbon atoms) may also be used. Specific examples are: tetraethylammonium iodide; (CH₃)₃ N.sup.⊕ (CH₂)₂ N.sup.⊕ (CH₃)₃.2I.sup.⊖ ; (CH₃)₃ N.sup.⊕ (CH₂)₆ N.sup.⊕ (CH₃)₃.2I.sup.⊖ ; N-methylpyridinium iodide; N-methylquinolinium iodide; N-hydroxyethylpyridinium chloride; N-hydroxypropylpyridinium bromide; N-methyl-2-hydroxymethylpyridinium iodide; N,N-dimethylpiperidinium iodide; N,N'-dimethylpyrazinium fluosulfate and γ-picolinium bisulfate.

Other bleaching accelerators are the water-soluble tertiary phosphines known from German Pat. No. 2,651,969, which preferably contain at least one cyanoethyl grouping. They have, for example, the formula ##STR47## in which W is --C_(r) H_(2r) CN, --C₄ H_(2r) NO₂ or a substituted or unsubstituted aryl radical or a heterocyclic radical, r is from 1 to 25, X is unsubstituted or substituted alkyl and Y is hydroxyalkyl, alkoxyalkyl, sulfoalkyl or aminoalkyl (alkyl in each case having 1 to 25, preferably 2 to 4, carbon atoms), phenyl, sulfophenyl or pyridyl. Preferred tertiary phosphines have the formula ##STR48## in which X₁ is --CH₂ CH₂ CN or --(CH₂)₂ OCH₃, Y₁ is --(CH₂)₂ SO₃.sup.⊖ M.sup.⊕, --(CH₂)₃ --SO₃.sup.⊖ M.sup.⊕, --(CH₂)₄ --SO₃.sup.⊖ M.sup.⊕, --(CH₂)₂ OCH₃ or --CH₂ N(C₂ H₅)₂, W₁ is --CH₂ CH₂ CN or phenyl and M⁺ is a cation, especially an alkali metal cation, for example the sodium or potassium cation.

Specific examples are the following compounds: the sodium salt of bis-(β-cyanoethyl)-2-sulfoethylphosphine, the sodium salt of bis-(β-cyanoethyl)-3-sulfopropylphosphine, the sodium salt of bis-(β-cyanoethyl)-4-sulfobutylphosphine, bis-(β-cyanoethyl)-2-methoxyethylphosphine, bis-(2-methoxyethyl)-(β-cyanoethyl)-phosphine, the sodium salt of (β-cyanoethyl)-phenyl-3-sulfopropylphosphine, (β-cyanoethyl)-phenyl-2-methoxyethylphosphine and bis-(2-methoxyethyl)-phenylphosphine.

For the silver development, baths of conventional composition can be employed, for example those which contain hydroquinone as the developer substance, with or without 1-phenyl-3-pyrazolidinone. The silver development bath can also already contain a bleaching catalyst.

The silver fixing bath can be made up in a known conventional manner. The fixing agent used is, for example, sodium thiosulfate or, advantageously, ammonium thiosulfate, if desired together with additives such as sodium bisulfite and/or sodium metabisulfite. Preparation examples

EXAMPLE 1 4-Formylamido-benzenesulfochloride

121.5 g of formanilide are added, a little at a time, to 340 ml of chlorosulfonic acid at 10° C. The reaction mixture is then warmed to 95` C. and is stirred at this temperature for 2.5 hours. When it has cooled, the reaction mixture is stirred into 2.5 kg of ice and the precipitate is filtered off with suction, thoroughly washed with ice water and dried. 172 g of 4-formylamidobenzenesulfochloride, of melting point 158°-160° C., are obtained.

4-Aminobenzenesulfonic acid N,N-diethylamide

120 g of ice and 32 g of sodium carbonate are added to a solution of 20.2 g of diethylamine in 240 ml of acetonitrile, 66 g of 4-formlyamidobenzenesulfochloride are then added, a little at a time, at a temperature of 5° to 10° C., and the mixture is stirred for 3 hours at 20° C. and finally for 3 hours at 70° C. The acetonitrile is evaporated under reduced pressure and the product is extracted with methylene chloride. The organic phase is washed with water and concentrated. Yield: 69 g of 4-formylamido-benzenesulfonic acid N,N-diethylamide. This crude product is dissolved in 500 ml of methanol, 50 ml of water and 90 ml of concentrated hydrochloric acid are added, and the reaction mixture is stirred for 5 hours at room temperature. It is then neutralised with sodium hydroxide solution and concentrated to half its volume. After addition of 210 ml of water, the product crystallises out. It is filtered off with suction, washed with water and recrystallised from ethanol. Yield: 44 g of 4-aminobenzenesulfonic acid N,N-diethylamide, of melting point 100°-102° C.

4-Amino-3,5-dibromobenzenesulfonic acid N,N-diethylamide

11.5 g of 4-aminobenzenesulfonic acid N,N-diethylamide are dissolved in 150 ml of methanol. The solution is cooled to 0° C. and 10 ml of concentrated hydrochloric acid are added. 5.1 ml of bromine in 50 ml of methanol, which has been saturated with sodium bromide, are then added dropwise. The yellow suspension is stirred for a further two hours at 20° C. and is then introduced into 1.5 liters of ice water. The mixture is neutralised with ammonia solution and the crude product is filtered off with suction, washed and recrystallised from ethanol. Yield: 13.1 g of white crystals of melting point 186°-187° C. The NMR spectrum and the CHN analysis correspond to the expected chemical structure.

EXAMPLE 2

The following sulfonamides are obtained analogously to Example 1:

    __________________________________________________________________________      ##STR49##                                                                                                          ##STR50##                                 Melting                             Melting                                    point (°C.)                                                                               R.sub.1    R.sub.2                                                                               point (°C.)                         __________________________________________________________________________     84-85                                                                                             ##STR51## H      97-99° C.                           Oil               C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                             79-81° C.                           Oil               (CH.sub.2).sub.3 OCH.sub.3                                                                H      78-79° C.                           160-169                                                                                           ##STR52##                                                                                 ##STR53##                                                                            178-180° C.                         --                (CH.sub.2).sub.3OCH.sub.3                                                                 C.sub.2 H.sub. 5                                                                      101-103° C.                         __________________________________________________________________________

EXAMPLE 3 4-Methylmercapto-nitrobenzene

28.3 g of methylmercaptan are dissolved in 500 ml of dimethylformamide at 0° C., under nitrogen. 37.4 g of potassium hydroxide, dissolved in 150 ml of ethanol, are then added dropwise at -10° C., after which 94.5 g of 4-chloronitrobenzene are added. The reaction mixture is warmed to 100° C. and stirred at this temperature for 8 hours. It is then stirred into 5 kg of ice water. The precipitate is filtered off with suction, washed, dried and recrystallised from methanol. Yield: 86.2 g of yellow crystals of melting point 71°-73.5° C.

In a similar manner, chloroinitrobenzene and hexylmercaptan give 4-hexylmercaptonitrobenzene.

2-Chloronitrobenzene and methylmercaptan analogously give 2-methylmercapto-nitrobenzene, and 2,4-dichloro-nitrobenzene and isobutylmercaptan give 2,4-diisobutylmercapto-nitrobenzene.

4-Methylsulfonyl-nitrobenzene

33.8 g of 4-methylmercapto-nitrobenzene in 180 ml of acetic acid are heated to 90° C. and a solution of 68 g of 49% peracetic acid solution in 50 ml of acetic acid is added slowly. The mixture is stirred for 30 minutes and poured into 1.2 liters of ice water. The product which precipitates is filtered off with suction, washed and dried. Yield: 38.2 g of white crystals of melting point 141°-144° C.

The following are obtained analogously: 4-hexylsulfonyl-nitrobenzene, melting point 44°-46° C.; 2-methylsulfonyl-nibrobenzene, melting point 104°-106° C., boiling point 215°-218° C. (0.25 mm Hg); 2,4-bis-isobutylsulfonylnitrobenzene, melting point 165°-167° C.

4-Methylsulfonyl-aniline

A Bechamp reduction of 16.1 g of 4-methylsulfonylnitrobenzene in 180 ml of 50% aqueous methanol gives 8.8 g of 4-methylsulfonylaniline of melting point 132°-134° C.

Using the method described above, 4-hexylsulfonylnitrobenzene gives 4-hexylsulfonylaniline, melting point 95°-97° C.; 2-methylsulfonyl-nitrobenzene gives 2-methylsulfonylaniline (melting point: 82°-83° C.) and 2,4-bis-isobutylsulfonylnitrobenzene gives 2,4-bis-isobutylsulfonylaniline by catalytic hydrogenation (melting point: 118°-120° C.).

4-Amino-3,5-dibromophenyl methyl sulfone

5.15 g of 4-methylsulfonyl-aniline are suspended in 40 ml of methanol and 2 ml of concentrated hydrochloric acid. 9.8 g of bromine in 20 ml of methanol, saturated with sodium bromide, are added dropwise at 0° to 5° C. The reaction mixture is stirred for 3 hours at room temperature and then for 30 minutes at 40° C., after which it is introduced into 600 ml of ice water. After having neutralised the mixture with ammonia solution, the precipitate is filtered off with suction, washed and dried. Yield: 9.3 g of white crystals of melting point 190°-192° C. On recrystallisation from toluene, the melting point rises to 192°-194° C.

Using an analogous method, 4-hexylsulfonylaniline gives 3,5-dibromo-4-hexylsulfonylaniline of melting point 192°-194° C.

EXAMPLE 4 (a) Diazo component

40.8 ml of chlorobenzene are added dropwise to 300 ml of chlorosulfonic acid. The yellow solution is slowly warmed to 150° C. and kept at this temperature for 17 hours. When it has cooled, 2 kg of ice are introduced. The precipitate is filtered off with suction, washed and dried. Yield: 31 g of white crystals of 4-chlorobenzene-1,3-di-(sulfochloride) of melting point 83°-86° C.

46.5 g of this sulfochloride are added, a little at a time, to a mixture of 120 ml of acetonitrile, 40.3 g of diethylamine, 60 g of ice and 16.2 g of sodium carbonate at a temperature of at most 20° C. After 2 hours, the temperature is raised to 70° C. and stirring is continued overnight. The suspension is filtered and the liquid organic phase is decanted and evaporated to dryness. The residue is recrystallised from 300 ml of methanol in the presence of animal charcoal. Yield: 32.1 g of white crystals of 4-chlorobenzene-1,3-disulfonic acid bis-N,N-diethylamide, of melting point 90°-91° C.

19.1 g of this product, in 50 ml of dioxane and 100 ml of concentrated ammonia are heated, after addition of a trace of iron trichloride, for 20 hours at 125° C. in a steel autoclave. The resulting 4-amino-benzene-1,3-disulfonic acid bis-N,N-diethylamide is extracted with chloroform and the organic phase is washed with water, dried over magnesium sulfate and evaporated. Yield: 13.7 g. After recrystallisation from ethanol, white crystals of melting point 137°-139° C. are obtained.

    ______________________________________                                         Analysis:                                                                      Calculated % C                                                                               46.26     Found % C 46.21                                        H              6.94                7.01                                        N             11.57               11.49                                        ______________________________________                                    

(b) Coupling component

6.5 g of N,N-dimethyl-m-phenylenediamine are dissolved in 50 ml of toluene and reacted with 6 g of isovaleryl chloride. The suspension is stirred for 2 hours at 40° C., cooled and treated with 26 ml of 2 N sodium hydroxide solution. The organic phase is decanted, washed with water and dried. After evaporation, 6.5 g of isovalerylamino-N,N-dimethylaniline of melting point 99°-101° C. are obtained.

    ______________________________________                                         Analysis:   Calculated % C                                                                             70.88   Found % C                                                                              71.03                                  (C.sub.13 H.sub.20 N.sub.2 O)                                                              H            9.16   H        8.99                                              N           12.72   N       12.59                                  ______________________________________                                    

(c) Azo dye 7.3 g of 4-aminobenzene-1,3-disulfonic acid bis-(N,N-diethylamide) in 160 ml of acetonitrile are treated with 2 ml of methanesulfonic acid, followed by 3 g of nitrosylsulfuric acid. After having been stirred for 20 minutes at room temperature, the reaction solution is introduced into 200 g of ice water. A solution of 4.4 g of the coupling component described under (b) in 40 ml of acetonitrile is added dropwise and the mixture is buffered with sodium acetate, whereupon a reddish oil separates out gradually. After one hour, the oil is taken up in chloroform and the organic phase is washed with water and evaporated. After recrystallising the residue from aqueous acetonitrile, 9 g of dye, of melting point 125°-127° C., are obtained.

    ______________________________________                                         Analysis:  Calculated % C                                                                              54.53  Found % C                                                                               54.43                                  (C.sub.27 H.sub.42 N.sub.6 O.sub.5 S.sub.2)                                               H             7.12  H         7.31                                             N            14.13  N        13.99                                  ______________________________________                                    

EXAMPLE 5

The following products are prepared analogously to Example 4a:

    __________________________________________________________________________                    ##STR54##                                                                                    ##STR55##                                                       Melting       Melting       % C    % H    % N                    R.sub.1                                                                               R.sub.2                                                                               point (°C.)                                                                           point (°C.)                                                                           Calc.                                                                             Found                                                                              Calc.                                                                             Found                                                                              Calc.                                                                             Found               __________________________________________________________________________     CH.sub.3 OC.sub.2 H.sub.4                                                             CH.sub.3 OC.sub.2 H.sub.4                                                             Oil           Oil           44.70                                                                             43.17                                                                              6.87                                                                              6.74                                                                                8.69                                                                              8.39               (CH.sub.3).sub.2 CH                                                                   (CH.sub.3).sub.2 CH                                                                   167-169       182-185       42.97                                                                             42.95                                                                              6.32                                                                              6.47                                                                               12.53                                                                             12.32               __________________________________________________________________________

EXAMPLE 6 (a) Diazo component

6.5 g of 4-aminobenzene-1,3-disulfonic acid bis-(N,N-diethylamide) in 400 ml of methanol are treated dropwise with 18 g of bromine at 20° C. After one hour, the mixture is warmed to 40° C. and is then stirred for a further 4 hours. When cold, the reaction mixture is poured into 4 kg of ice water and 60 ml of concentrated ammonia solution are added. The precipitate is filtered off with suction, washed and dried. Yield: 29 g of 4-amino-5-bromobenzene-1,3-disulfonic acid bis-(N,N-diethylamide) of melting point 87°-89° C.

    ______________________________________                                         Analysis:   Calculated % C                                                                             38.01  Found % C                                                                               37.97                                  (C.sub.14 H.sub.24 N.sub.3 S.sub.2 O.sub.4 Br)                                             H            5.47  H         5.43                                              N            9.50  N         9.47                                  ______________________________________                                    

(b) Azo dye

13.2 g of the diazo component from Example 6(a), in 250 ml of acetonitrile, are diazotised analogously to Example 4. After 80 minutes, the diazonium solution is poured onto 300 g of ice, and a solution of 7.5 g of 2-[5-acetamino-2-methoxyphenylamino]-1-methoxypropane in 45 ml of acetonitrile is added dropwise, and the mixture is buffered by adding sodium acetate. After 45 minutes, the dye is extracted with chloroform. The organic phase is washed with water, dried, treated with silica gel and evaporated. After recrystallisation from aqueous acetonitrile, 6 g of dye, of melting point 160°-162° C., are obtained.

    ______________________________________                                         Analysis (C.sub.27 H.sub.41 BrN.sub.6 O.sub.7 S.sub.2):                        Calculated % C                                                                               45.96     Found % C 45.97                                        H              5.86     H          5.84                                        N             11.91     N         11.91                                        ______________________________________                                    

EXAMPLE 7

3.9 g of dye from Example 6, in 80 ml of N-methylpyrrolidone, are treated with 0.8 g of copper cyanide. The mixture is stirred for 45 minutes at 50° C. and is then introduced into 700 ml of water. The precipitate is filtered off with suction, washed and dissolved in chloroform, and this solution is washed with 40% ammonium thiocyanate solution and then with water. The solvent is evaporated and the residue is dissolved in acetonitrile and reprecipitated with water. The dye is filtered off with suction and dried. Yield: 2.5 g (melting point 159°-172° C.).

    ______________________________________                                         Analysis:  Calculated % C                                                                             51.60  H 6.35  N 15.05                                  (C.sub.28 H.sub.41 N.sub.7 O.sub.7 S.sub.2)                                               found C     51.54  H 6.37  N 14.74                                  ______________________________________                                    

The dyes of the general formula ##STR56## listed in Table 1 are prepared in a similar manner.

    TABLE I       Dye           No. X.sub.1 Y.sub.1 Z.sub.1 R.sub.3 R.sub.4 R.sub.1      R.sub.2 λ.sup.CHCl.sbsp.3.sub.max ε.sub.mol λ.sup.G      el.sub.max        101       ##STR57##       NHC.sub.2 H.sub.4 CN H H H Br H 414 28530 444  102 " " H CON(CH.sub.2      CH.sub.2 OCH.sub.3).sub.2 H H H 410 24270 420 103 " " H CO.sub.2      CH.sub.3 H H H 411 25230 433 104 " " H CO.sub.2 C.sub.2 H.sub.4       OCH.sub.3 H H H 411 24150 433 105 " " H Br H H Br 401 23070 421 106 " "      H Br H C.sub.2 H.sub.5 Br 403 20160 423 107 " " H Br H CH.sub.3 Br 400      21740 420 108 " "  H CH.sub.3 H Br CH.sub.3 384 21310 410 109 " NHCH(CH.s      ub.3)CH.sub.2 OCH.sub.3 H Br H H Br 418 23090 433 110 " " H Br H Br Br      424 23390 444 111 " " H Br H Cl Br 423 25280 443 112 " " H Br H C.sub.2      H.sub.5 Br 418 22270 432 113 " " H Br H CH.sub.3 Br 417 22270 432 114 "      " OCH.sub.3 H H NO.sub.2 H 535 35480 538 115 " " OCH.sub.3 CN H H CN 568      44790 537 116 " " OCH.sub.3 CN H CO.sub.2 (C.sub.2 H.sub.4 O).sub.2 Et      CN 565 48880 555 117 " " OCH.sub.3 CN H SO.sub.2 NH(CH.sub.2).sub.3      OCH.sub.3 H 547 38520 545 118 " " OCH.sub.3 SO.sub.2 CH.sub.3 H SO.sub.2      N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 SO.sub.2 CH.sub.3 566 40610 565 119      " N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 CN H p-ClC.sub.6 H.sub.4 CO      NO.sub.2 633 72510 634 120 " " OCH.sub.3 CN H CO.sub.2 C.sub.2 H.sub.5      NO.sub.2 622 64390 626 121 " " OCH.sub.3 CN H SO.sub.2       NH(CH.sub.2).sub.3 OCH.sub.3 CN 627 84260 626 122 " " OCH.sub.3 CN H "      NO.sub.2 622 66880 622 123 " " OCH.sub.3 CN H SO.sub.2 N(C.sub.2      H.sub.5).sub.2 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 623 55490 627 124 " "      OCH.sub.3 CN H SO.sub.2 N(CH.sub.2 CH.sub.2 OCH.sub.3).sub.2 CN 625      79230 627       125 " " OCH.sub.3 CN H      ##STR58##       CN 630 83330 630  126 " " OCH.sub.3 CN H CN NO.sub.2 630 78220 631 127      " N(CH.sub.3).sub.2 H Br H H Br 433 24290 440 128 " " H Br H CH.sub.2      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 Br 431 24510 443 129 " " H Br H      C.sub.4 H.sub.9 Br 430 24380 441 130 " " H Br H C.sub.2 H.sub.5 Br 426      22610 439 131 " " H CN H H CN 533 38050 534 132 " " H CN H CN H 527      49600 525 133 " " H H CO.sub.2 C.sub.2 H.sub.5 CN CN 539 54000 538 134 "      " H CN H NO.sub.2 CN 620 72170 622 135 " " H CN CO.sub.2 C.sub.2 H.sub.5      CN CN 607 58000 570       136      ##STR59##       NHC.sub.2 H.sub.4 CN H Br H H Br 402 23010 420  137 " " H Br H C.sub.2      H.sub.5 Br 402 24640 419 138 " " H Br H CH.sub.3 Br 402 24730 419 139      NHCO(CH.sub.2).sub.3 CO.sub.2 C.sub.2 H.sub.5 N(C.sub. 2 H.sub.5).sub.2      OCH.sub.3 CN H H CN 592 52320 595 140 " "  CN H CN NO.sub.2 632 83510      631 141 N(CH.sub.3)COCH.sub.3 NHC.sub.2 H.sub.4 CN OCH.sub.3 H H      CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 H 423 27080 444 142      NHCO.sub.2 C.sub.2 H.sub.5 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 CN H      SO.sub.2 NH(CH.sub.2).sub.3 OCH.sub.3 CN 623 75340 624 143 NHCO.sub.2      C.sub.4       H.sub.9 " OCH.sub.3 CN H " CN 623 73610 620 144 N(CH.sub.3)SO.sub.2      CH.sub.3 NHC.sub.2 H.sub.4 CN OCH.sub.3 H H CO.sub.2 CH.sub.2 CH(C.sub.2      H.sub.5)C.sub.4       H.sub.9 H 434 26840 451 145 NHCOCH.sub.3 NHCH(CH.sub.3)CH.sub.2      OCH.sub.3 OCH.sub.3 SO.sub.2 CH.sub.3 H SO.sub.2 N(C.sub.2       H.sub.5).sub.2 SO.sub.2 CH.sub.3 567 39550 569 146 " NHCH.sub.2      C(CH.sub.3).sub.2 NO.sub.2 H CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3 H H H      415 24560 432 147 " NHCH(CH.sub.3)CH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.3      NO.sub.2 H CN H 556 44120 557 148 " N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 H      H NO.sub.2 H 547 24410 552 149 " " OCH.sub.3 SO.sub.2       NHCH(CH.sub.3).sub.2 H SO.sub.2 NHCH(CH.sub.3).sub.2 H 553 39390 547      150 " " OCH.sub.3 CN H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 SO.sub.2      N(C.sub.2 H.sub.5).sub.2 623 44130 626 151 " " OCH.sub.3 CN H " CN 626      113100 627 152 " " OCH.sub.3 CN H SO.sub.2 N(CH.sub.2 CH.sub.2       OCH.sub.3).sub.2 CN 624 71650 626 153 NHCOCH(CH.sub.3).sub.2 NHC.sub.2      H.sub.4 CN H PO(OC.sub.2 H.sub.5).sub.2 H H H 419 17840 439  154       ##STR60##       N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 H Br OC.sub.4 H.sub.9 CN 531 34900      531  155 " N(CH.sub.3).sub.2 H Br H OCH.sub.2 CH.sub.2       CH(CH.sub.3).sub.2 Br 429 26400 418 156 " NHCH(CH.sub.3)CH.sub.2      OCH.sub.3 H CN H NO.sub.2 CH.sub.3 551 38160 563             157       ##STR61##       " OCH.sub.3 CN H H CN 567 44680 570                  158      ##STR62##       NHC.sub.2 H.sub.4 CN H Br H CH.sub.3 CH.sub.3 390 20370 413  159      CH.sub.3       ##STR63##       H H H CO.sub.2 C.sub.2 H.sub.5 H 438 27770 451  160 CH.sub.3 " H H H      SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H 440 27850 451 161 CH.sub.3      " H Br H H Br 406 21180 413 162 OCH.sub.3 NHSO.sub.2 C.sub.6 H.sub.4      CH.sub.3 OCH.sub.3 H H CO.sub.2 C.sub.2 H.sub.5 H 417 16330 425  163 OH      H       ##STR64##       H H OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 H 403 10820 421  164 OH      H " H H C.sub.4 H.sub.9 H 408  6960 427 165 OH H " H H OC.sub.4 H.sub.9      H 400 11280 422 166 OH H OCH.sub.2 CH(CH.sub.3).sub.2 H H OC.sub.4      H.sub.9 H 428  9720 431 167 OH H " H OC.sub.2 H.sub.4 OCH.sub.3 OC.sub.2      H.sub.4 OCH.sub.3 H 434  10860 438 168 OH H CH.sub.2 CO(C.sub.2 H.sub.4      O).sub.2 OCH.sub.3 H H SO.sub.2 C.sub.6 H.sub.4 OH H 412 11620 407 169      OH H (OC.sub.2 H.sub.4).sub.2 OCH.sub.3 H H OC.sub.4 H.sub.9 H 420  9410      430 170 OH H CH.sub.3 H H NHCOCH.sub.3 H 400 13240 403  171 OH H      C(CH.sub.3).sub.2 C.sub.2       H.sub.5 H H      ##STR65##       H 401 16110 405  172 OH H " H H CO.sub.2 C.sub.2 H.sub.5 H 411  8700      410 173 OH H " H H SO.sub.2 C.sub.6 H.sub.13 H 417  7400 412 174 OH H "      H CO.sub.2 C.sub.2 H.sub.5 H OCH.sub.3 405 10350 410 175  NHCOCH.sub.2      CH(CH.sub.3).sub.2 H H H OC.sub.4 H.sub.9 H 406  23080 400 176 OH "      OCH.sub.3 H H NHCOCH.sub.2 CH(CH.sub.3).sub.2 H 452 21770 460 177 OH      NHCOCH.sub.2 CH(CH.sub.2).sub.2 OCH.sub.3 H H OCH.sub.2       CH(CH.sub.3).sub.2 H 434 21300 451 178 OH " OCH.sub.3 H H OCH.sub.2      CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 H 444 21400 452 179 OH " OCH.sub.3 H      H (OC.sub.2 H.sub.4).sub.2       OCH.sub.3 H 445 20900 449 180 OH NHCOCH(C.sub.2 H.sub.5)C.sub.4 H.sub.9      OCH.sub.3 H H OCH.sub.2 CH(CH.sub.3).sub.2 H 445 20300 451 181 OH "      OCH.sub.3 H H OCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 H 447 19800      451 182 OH N(C.sub.4 H.sub.9)COCH.sub.3 OCH.sub.3 H H OCH.sub.2       CH(CH.sub.3).sub.2 H 418 12400 423 183 OH " OCH.sub.3 H OC.sub.2      H.sub.5 OC.sub.2 H.sub.5 H 436 14800 442 184 OH NHCO(OC.sub.2       H.sub.4).sub.2 OCH.sub.3 OCH.sub.3 H H OCH.sub.2 CH(CH.sub.3).sub.2 H      444 21400 447 185 OH NHPO(OC.sub.4 H.sub.9).sub.2 OCH.sub.3 H H " H 444      20800 449 186 OH OH C.sub.3 H.sub.7 H H OC.sub.4 H.sub.9 H 396 21870 401      187 OH OCH.sub.3 NHCOCH.sub.2 CH(CH.sub.2).sub.2 H H OCH.sub.2       CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 H 429 15800 439 188 OH OCH.sub.3      OCH.sub.3 H H OCH.sub.2 CH(CH.sub.3).sub.2 H 443 17400 447 189 OH      OCH.sub.3 C.sub.3 H.sub.7 H H OC.sub.4 H.sub.9 H 397 19800 400 190 OH      OC.sub.3 H.sub.7 CH.sub.3 H H SO.sub.2 C.sub.6 H.sub.13 H 405 17100 416      191 OH OC.sub.3 H.sub.7 CH.sub.3 H H OCH.sub.2 CH(CH.sub.3).sub.2 H 400      19700 403 192 OH " CH.sub.3 H H C.sub.4 H.sub.9 H 396 16400 400 193 OH "      CH.sub.3 SO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H SO.sub.2 CH.sub.2      CH(CH.sub.3).sub.2 H 462 10400 452 194 OH " CH.sub.3 Br H SO.sub.2      C.sub.6       H.sub.13 Br 410 12900 410 195 OH " CH.sub.3 OCH.sub.3 H OCH.sub.2      CH(CH.sub.3).sub.2 H 436 19600 439       196      ##STR66##       NHC.sub.2 H.sub.4 CN H H CO.sub.2 C.sub.2 H.sub.5 H H 411 28270 441      197 " " H Br OC.sub.2 H.sub.5 CH.sub.3 Br 403 21140 411       198      ##STR67##       ##STR68##       OCH.sub.3 CH.sub.3 SO.sub.2 H NO.sub.2 NO.sub.2 622 46750 632  199 "      N(C.sub.2 H.sub.5).sub.2 OC.sub.2 H.sub.4 OCH.sub.3 CF.sub.3 H NO.sub.2      CN 651 82350 655 200 " " " CN CO.sub.2 CH.sub.3 NO.sub.2 CN 661 98310      658       201      ##STR69##       " OCH.sub.3 CN H CHC(CN).sub.2 CN 640 97500 639  202 " " OCH.sub.3 CN H      NO.sub.2 NO.sub.2 655 89270 654 203 " N(CH.sub.3).sub.2 H CN H SO.sub.2      N(C.sub.2 H.sub.5).sub.2 SO.sub.2 N(C.sub. 2 H.sub.5).sub.2 557 41960      561                  204      ##STR70##       N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 CN H CN NO.sub.2 631 79060 630  205      " " OCH.sub.3 CN H NO.sub.2 CN 655 89070 656       206      ##STR71##       ##STR72##       OCH.sub.3 CN H H CN 552 37690 546  207 NHCOCH.sub.3 N(C.sub.2       H.sub.5).sub.2 OCH.sub.3 Br H NO.sub.2 NO.sub.2 627 48900 625 208 " "      OCH.sub.3 CF.sub.3 H NO.sub.2 CN 649 72400 652 209 " " OCH.sub.3 H CN H      CN 559 36000 554  210 OH NHCO(OC.sub.2       H.sub.4).sub.2 OCH.sub.3 OCH.sub.3 H H       ##STR73##       H 444 21400 449  211 OH N(C.sub.3 H.sub.7).sub.2 OCH.sub.3 CN H C.sub.4      H.sub.9 CN 565 31400 566 212 NHCOC.sub.2 H.sub.5 N(C.sub.2       H.sub.5).sub.2 OC.sub.2 H.sub.4 OCH.sub.3 CN H NO.sub.2 SO.sub.2      CH.sub.3 652 96060 660       213      ##STR74##       N(C.sub.2 H.sub.5).sub.2 OC.sub.2 H.sub.4 OCH.sub.3 CN H NO.sub.2      SO.sub.2 CH.sub.3 652 78860 659  214 NHCOC.sub.2       H.sub.5      ##STR75##       OC.sub.2 H.sub.4 OCH.sub.3 CN H CH.sub.3 CN 559 39410 535       215      ##STR76##       " OCH.sub.3 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H SO.sub.2 CH.sub.3      SO.sub.2 N(C.sub.2       H.sub.5).sub.2 549 26450 545                            Dye No. X.sub.1 Y      .sub.1 Z.sub.1 R.sub.1 R.sub.2 R.sub.3 R.sub.4 λ.sup.CHCl.sbsp.3.s      ub.max ε.sub.mol λ.sup.Gel.sub.max        216 NHCOCH.sub.2       CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H C(CH.sub.3).sub.3 H H H 453      30700 458 217 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H      O(CH.sub.2).sub.3 CH.sub.3 H H H 458 31600 460 218 CH.sub.3 N(C.sub.2      H.sub.5)CH.sub.2 CH.sub.2 OCOCH.sub.3 H Cl H H H 421 27400 430 219      NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H Br Br Br H 400      21500 429 220 NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H Cl      Br Br H 412 23800 435 221 NHCOCH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H      H Br Br H 402 23000 419 222 NHCOCH.sub.2       CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H CH.sub.3 Br Br H 422 20800 440      223 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H Cl Br Br H 439      23700 453 224 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H      C.sub.2 H.sub.5 Br Br H 426 22600 437 225 NHCOCH.sub.2       CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H (CH.sub.2).sub.3 CH.sub.3 Br Br      H 430 24400 438 226 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(CH.sub.3).sub.2 H      OCH.sub.2 CH.sub.2       CH(CH.sub.3).sub.2 Br Br H 429 26400 430 227 NHCOCH.sub.2       CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H CH.sub.3 CH.sub.3 Br H 390      20400 410 228 NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H Br      CH.sub.3 CH.sub.3 H 384 21300 409 229 NHCOCH.sub.2 CH(CH.sub.3).sub.2      NHC.sub.2 H.sub.4 CN H CH.sub.2 CH(CH.sub.3).sub.2 Br Br H 403 23200 422      230 NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H H Br H H 416      28800 433 231 NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H      CH.sub.3 Br Br OC.sub.2 H.sub.5 403 21100 406 232 NHCOCH.sub.2       CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H CH.sub. 3 Br Br OC.sub.2      H.sub.4 CH(CH.sub.3).sub.2 401 23700 410 233 NHCOCH.sub.2       CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H CH.sub.3 Br Br OCH.sub.3 402      22200 406 234 NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H H H      H CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 412 26000 455 235 NHCOCH.sub.2      CH(CH.sub.3).sub.2 NHC.sub.2 H.sub.4 CN H H CON(C.sub.2 H.sub.4       OCH.sub.3).sub.2 H H 410 24270 420 236 OH NHCOCH.sub.3 OCH.sub.3      O(C.sub.2 H.sub.4 O).sub.2 CH.sub.3 H H H 441 20400 448 237 OH H      OCH.sub.2 CH(CH.sub.3).sub.2 OC.sub.2 H.sub.4 OCH.sub.3 H H OC.sub.2      H.sub.4 OCH.sub.3 434 10900 438       238 OH      ##STR77##       OCH.sub.3 CH.sub.2 CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 H H H 420  9500      423       239 OH      ##STR78##       OCH.sub.3 OC.sub.2 H.sub.4 OCH.sub.3 H H OC.sub.2 H.sub.4 OCH.sub.3 436      14800 443  240 OH OCH.sub.3 NHCOCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.2      CH(CH.sub.3).sub.2 H H H 429 15800 439 241 OH OCH.sub.2 CH.sub.2      CH.sub.3 CH.sub.3 OCH.sub.2 CH(CH.sub.3).sub.2 OCH.sub.3 H H 436 19600      439 242 NHSO.sub.2 C.sub.6 H.sub.13 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3      CN CN CN H 624 776600 625 243 CH.sub.3 N(C.sub.2 H.sub.5)C.sub.2 H.sub.4      OCOCH.sub.3 H SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 CN CN H 542      42500 550 244 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2      OCH.sub.3 NO.sub.2 CN CN H 657 95220 656 245 NHCOOC.sub.2 H.sub.5      N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 SO.sub.2 NHC.sub.3 H.sub.6 OCH.sub.3      CN CN H 623 75340 624 246 NHCOCH.sub.2       CH(CH.sub.3).sub.2 NHCH(CH.sub.3)CH.sub.2 OCH.sub.3 OCH.sub.3 CH.sub.2      CN CN H 564 43110 567 247 NHCO(CH.sub.2).sub.3 COOC.sub.2 H.sub.5      N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 NO.sub.2 CN CN H 654 97420 655 248      NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3      NO.sub.2 NO.sub.2 CN H 655 89270 654 249 NHCOCH.sub.3 NHCH(CH.sub.3)CH.su      b.2 CH(CH.sub.3).sub.3 OCH.sub.3 CH.sub.3 CN CN H 567 45460 571 250      NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 Br CN      CN NO.sub.2 630 81910 633 251 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(C.sub.2      H.sub.5).sub.2 OCH.sub.3 NO.sub.2 CN CN CH.sub.3 643 84960 641 252      NHCOCH.sub.2 CH(CH.sub.3).sub.2 NHCH(CH.sub.3)CH.sub.2       CH(CH.sub.3).sub.2 OCH.sub.3 OC.sub.2 H.sub.4 CH(CH.sub.3).sub.2 CN CN      H 566 43360 570 253 NHCOC.sub.2 H.sub.5 NHCH(CH.sub.3)CH.sub.2 OC.sub.2      H.sub.4 OCH.sub.3 H CN CN H 568 42660 564 254 NHCOCH.sub.2       CH(CH.sub.3).sub.2 N(C.sub.4 H.sub.9).sub.2 OCH.sub.3 NO.sub.2 CN CN H      659 92480 659 255 NHCOCH.sub.2       CH(CH.sub.3).sub.2 NHCH(CH.sub.3 )CH.sub.2 OCH.sub.3 OCH.sub.3 CH.sub.3      CN CN OCH.sub.3 568 49840 570 256 NHCOC.sub.2 H.sub.5 N(C.sub.2       H.sub.5).sub.2 OC.sub.2 H.sub.4 OCH.sub.3 NO.sub.2 CN CN CO.sub.2      CH.sub.3 663 92490 663 257 NHCOC.sub.2 H.sub.5 N(C.sub.2 H.sub.5).sub.2      OCH.sub.3 SO.sub.2 NHC.sub.3 H.sub.6 OCH.sub.3 CN NO.sub.2 H 623 61370      622 258 NHCOCH.sub.2 CH(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2      OC.sub.2 H.sub.5 NO.sub.2 CN CN H 659 97310 658 259 NHCOC.sub.2 H.sub.4      OC.sub.2 H.sub.5 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 NO.sub.2 CN CN      CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3 660 99710 662 260 NHCOCH.sub.3      N(C.sub.2 H.sub.5).sub.2 OCH.sub.2 NO.sub.2 CF.sub.3 CN H 649 73900 652      261 NHCOC.sub.2 H.sub.5 NHCH(CH.sub.3)CH.sub.2 OCH.sub.3 OC.sub.2      H.sub.4 OCH.sub.3 NO.sub.2 CN CN CO.sub.2 CH.sub.3 634 73490 638 262      NHCOC.sub.2 H.sub.5 N(C.sub.3 H.sub.7).sub.2 OC.sub.2 H.sub.4 OCH.sub.3      NO.sub.2 SO.sub.2 CH.sub.3 CN H 651 68690 657 263 NHCOCH.sub.2       CH(CH.sub.3).sub.2 N(C.sub.2 H.sub.5).sub.2 OC.sub.2 H.sub.5 SO.sub.2      CH.sub.2       CH(CH.sub.3).sub.2 CN CN NO.sub.2 636 80970 637 264 NHCOCH.sub.3      N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 NO.sub.2 Cl NO.sub.2 H 628 50400 621      265 NHCOCH.sub.3 NHCH(CH.sub.3)CH.sub.2 OCH.sub.3 OCH.sub.3 NO.sub.2      NO.sub.2 NO.sub.2 H 615 48130 615

Use examples EXAMPLE 8

34 mg of the dye of the formula ##STR79## are dissolved in 2 ml of a 9:1 mixture of ethyl acetate and tricresyl phosphate, and the solution is added to a mixture of 6.6 ml of a 6% aqueous gelatin solution, 0.9 ml of distilled water and 0.5 ml of an 8% solution of sodium dibutylnaphthalenesulfonate, and emulsified therein by ultrasonics.

2.5 ml of the resulting emulsion are mixed with 5 ml of water, 2.5 ml of an unsensitised gelatin/silver bromide-iodide emulsion containing about 22 g of silver/kg of gelatin, and 1 ml of a 1% solution of a hardener of the formula ##STR80## This mixture is cast on an opaque triacetate base (size 13×18 cm) and dried. The resulting light-sensitive material is exposed behind a step wedge and is processed at 24° C., as follows:

    ______________________________________                                         Developing            6 minutes                                                Washing               4 minutes                                                Silver bleaching and dye bleaching                                                                   6 minutes                                                Washing               2 minutes                                                Fixing                8 minutes                                                Washing               6 minutes                                                Drying                                                                         ______________________________________                                    

The developer baths and fixing baths are conventional baths, as used in black-and-white photography. The silver dye bleach bath has the following composition per liter of solution:

    ______________________________________                                         Sulfamic acid            100 g                                                 m-Nitrobenzenesulfonic acid                                                                             10 g                                                  Potassium iodide         6 g                                                   2,3,6-Trimethylquinoxaline                                                                              2 g                                                   4-Mercaptobutyric acid   1 g                                                   ______________________________________                                    

A counter-imagewise yellow wedge, which is bleached completely white where originally the silver density was highest, is obtained. The image is distinguished by great brilliance and light-fastness.

EXAMPLE 9

25 mg of the dye of the formula ##STR81## are incorporated into a light-sensitive photographic material analogously to the above example.

After exposure, the material is processed at 30° C., as follows:

    ______________________________________                                         Developing            3 minutes                                                Washing               1 minutes                                                Silver bleaching and dye bleaching                                                                   5 minutes                                                Washing               1 minutes                                                Fixing                4 minutes                                                Washing               6 minutes                                                Drying                                                                         ______________________________________                                    

The baths used have the composition mentioned above. A brilliant, light-fast yellow wedge is obtained, which in the area of maximum silver density is bleached completely white.

EXAMPLE 10

14 mg of the dye of the formula ##STR82## are dissolved in 2 ml of a 9:1 mixture of ethyl acetate and Reofos 65 (trisisopropylphenylphosphate) and the solution is then emulsified with 7 ml of a 5% gelatin solution and 0.5 ml of an 8% aqueous solution of sodium dibutylnaphthalenesulfonate, to give a homogeneous mixture. 5 ml of water, 98 ml of an unsensitised gelatin/silver bromide-iodide emulsion, containing about 22 g of silver per kg of gelatin, 1.7 ml of a 4% gelatin solution and 1 ml of a 1% hardener solution are added to 2.5 ml of this dye emulsion. The mixture is cast on an opaque triacetate film of size 13×18 cm and dried. The resulting light light-sensitive material is exposed to white light behind a step wedge and is processed at 30° C., as follows:

    ______________________________________                                         Developing            3 minutes                                                Washing               1 minutes                                                Silver bleaching and dye bleaching                                                                   5 minutes                                                Washing               1 minutes                                                Fixing                4 minutes                                                Washing               6 minutes                                                Drying                                                                         ______________________________________                                    

The developer bath contains the following per liter of solution:

    ______________________________________                                         Sodium sulfite           50 g                                                  1-Phenyl-3-pyrazolidone  0.2 g                                                 Hydroquinone             6 g                                                   Sodium carbonate         35 g                                                  Potassium bromide        4 g                                                   Benzotriazole            0.3 g                                                 ______________________________________                                    

The silver dye bleach bath contains the following per liter of solution:

    ______________________________________                                         Concentrated sulfuric acid                                                                              28    ml                                              Sodium m-nitrobenzenesulfonate                                                                          10    g                                               Potassium iodide         6     g                                               Sodium salt of bis-(2-cyanoethyl)-                                             (2-sulfoethyl)-phosphine 3     g                                               2,3-Dimethylquinoxaline  1.5   g                                               ______________________________________                                    

The fixing bath contains the following per liter of solution:

    ______________________________________                                         Sodium thiosulfate      200 g                                                  Sodium metabisulfite    20 g                                                   ______________________________________                                    

A brilliant, light-fast magenta wedge is obtained, which is bleached completely white in the areas where the silver density was originally highest.

EXAMPLE 11

50 mg of the dye of the formula ##STR83## are dissolved in 2 ml of ethylene chloride and 0.2 ml of tricresyl phosphate. 7 ml of 5% gelatin solution and 0.5 ml of an 8% aqueous solution of sodium dibutylnaphthalenesulfonate are added and this mixture is emulsified until homogeneous. The dye emulsion is mixed with 7 ml of a 4% gelatin solution, 16 ml of water, 3 ml of a stabilised silver halide emulsion which contains 24 g of silver per kg of gelatin, and 4 ml of a 1% hardener solution. This emulsion is cast on 0.1 m² of an opaque base, solidified and dried.

A strip, cut to size 3.5×18 cm, is exposed for 1 second to white light (200 Lux/cm²) under a step wedge and through a blue filter (Kodak 26+47B). The strip is then processed at 24° C., as follows:

    ______________________________________                                         Developer bath    6 minutes                                                    Washing           4 minutes                                                    Silver dye bleach bath                                                                           6 minutes                                                    Washing           2 minutes                                                    Fixing            8 minutes                                                    Washing           6 minutes                                                    Drying                                                                         ______________________________________                                    

The developer bath used has the composition given in U.S. Pat. No. 4,141,734.

The silver dye bleach bath used is a solution which, per liter, contains the following components:

    ______________________________________                                         Concentrated sulfuric acid                                                                               28    ml                                             Sodium iodide             9     g                                              Disodium salt of 4-nitrophenol-2-                                                                        6     g                                              sulfonic acid                                                                  6-Methoxy-2,3-dimethylquinoxaline                                                                        1     g                                              Sodium salt of bis-(2-cyanoethyl)-                                                                       3     g                                              (2-sulfoethyl)-phosphine                                                       ______________________________________                                    

In addition, a conventional fixing bath, containing 200 g of sodium thiosulfate per liter of solution, is used.

A brilliant, light-fast cyan wedge is obtained, which is bleached completely white in the area which originally had the greatest silver density.

The other dyes of Table I can be incorporated analogously into the colour-photographic material according to the invention. 

What is claimed is:
 1. A colour-photographic recording material for the silver dye bleach process which contains at least one diffusion-resistant, bleachable and oil-soluble monoazo dye dissolved in a high-boiling organic solvent in at least one silver halide emulsion layer or in a colloid layer adjoining the silver halide emulsion layer, and wherein the dye has the formula ##STR84## in which R₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, substituted or unsubstituted alkoxy having 1 to 16 carbon atoms, substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, substituted or unsubstituted aliphatic acyl having 2 to 5 carbon atoms, substituted or unsubstituted benzoyl, substituted or unsubstituted carbalkoxy having 2 to 20 carbon atoms or --NV₁ COU₁, in which V₁ is hydrogen or alkyl having 1 to 4 carbon atoms and U₁ is substituted or unsubstituted alkyl having 1 to 12 carbon atoms or substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, or R₁ is N-alkyl-substituted or N,N-dialkyl-substituted carboxamido or sulfonamido, in which each alkyl moiety has 1 to 12 carbon atoms and can be substituted further, or R₁ is substituted or unsubstituted alkylsulfone having 1 to 12 carbon atoms, substituted or unsubstituted arylsulfone, substituted or unsubstituted aryloxy or substituted or unsubstituted arylsulfonic acid ester, or is hydroxyl, cyano, nitro or halogen, R₂ is hydrogen, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted, or R₂ is substituted or unsubstituted alkylsulfone having 1 to 6 carbon atoms, substituted or unsubstituted arylsulfone or substituted or unsubstituted aryloxy, or is cyano, nitro or halogen, R₃ is hydrogen, substituted or unsubstituted alkyl or alkoxy having 1 to 4 carbon atoms, substituted or unsubstituted phenoxy, or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted, or R₃ is substituted or unsubstituted alkylsulfone having 1 to 4 carbon atoms, substituted or unsubstituted phenylsulfonic acid ester, cyano, nitro, halogen, substituted or unsubstituted carbalkoxy having 1 to 16 carbon atoms, or --P(O)(OT¹)₂, in which T¹ is alkyl having 1 to 4 carbon atoms, R₄ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 16 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 12 carbon atoms and can be substituted, or R₄ is --NQ₁ COT₁, in which Q₁ is hydrogen or alkyl having 1 or 2 carbon atoms and T₁ is substituted or unsubstituted alkyl having 1 to 4 carbon atoms, or R₄ is substituted or unsubstituted alkylsulfone having 1 to 12 carbon atoms, substituted or unsubstituted arylsulfone hydroxyl, cyano, nitro or halogen, R₅ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms or substituted or unsubstituted carbalkoxy having 2 to 13 carbon atoms, X₁ is hydrogen, substituted or unsubstituted alkyl or alkoxy having 1 to 6 carbon atoms or --NL₁ CO--M₁, in which L₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 4 carbon atoms and M₁ is substituted or unsubstituted alkyl or alkoxy having 1 to 24 carbon atoms, or X₁ is substituted or unsubstituted alkylsulfonylamino having 1 to 25 carbon atoms or hydroxyl, Y₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 12 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted, or Y₁ is substituted or unsubstituted arylsulfonylamino or --NE₁ COG₁, in which E₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 8 carbon atoms and G₁ is substituted or unsubstituted alkyl having 1 to 12 carbon atoms or substituted or unsubstituted alkoxy having 1 to 4 carbon atoms, or Y₁ is --NE₁ P(O)(OG¹)₂, in which E₁ is as defined above and G¹ is alkyl having 1 to 12 carbon atoms, or Y₁ is halogen or hydroxyl, Z₁ is hydrogen, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms or --NA₁ COD₁, in which A₁ is hydrogen or substituted or unsubstituted alkyl having 1 to 8 carbon atoms and D₁ is substituted or unsubstituted alkyl having 1 to 18 carbon atoms, or Z₁ is substituted or unsubstituted acyl having 2 to 9 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 19 carbon atoms, substituted or unsubstituted alkylsulfonylamino having 1 to 6 carbon atoms, halogen or the atoms which together with Y₁ form a substituted or unsubstituted 5-membered or 6-membered, saturated or unsaturated ring which can contain 1 or 2 hetero-atoms, and W₁ is hydrogen, substituted or unsubstituted alkyl or alkoxy, each having 1 to 4 carbon atoms, or halogen.
 2. A colour-photographic recording material according to claim 1, which contains a dye of the formula ##STR85## in which R₆ is hydrogen, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 16 carbon atoms, substituted or unsubstituted alkenyl having 2 to 4 carbon atoms, substituted or unsubstituted aliphatic acyl having 2 or 3 carbon atoms, substituted or unsubstituted benzoyl, substituted or unsubstituted carbalkoxy having 2 to 16 carbon atoms, or --NV₂ COU₁, in which V₂ is hydrogen or alkyl having 1 or 2 carbon atoms and U₁ is as defined in claim 1, or R₆ is N-alkyl-substituted or N,N-dialkyl-substituted carboxamido or sulfonamido, in which each alkyl moiety contains 1 to 10 carbon atoms and can be substituted further, or R₆ is substituted or unsubstituted alkylsulfone having 1 to 8 carbon atoms, substituted or unsubstituted phenylsulfone, substituted or unsubstituted phenoxy or substituted or unsubstituted phenylsulfonic acid ester, or is hydroxyl, cyano, nitro or halogen, R₇ is hydrogen, substituted or unsubstituted alkyl having 1 to 8 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety contains 1 to 8 carbon atoms and can be substituted, or R₇ is substituted or unsubstituted alkylsulfone having 1 to 6 carbon atoms, substituted or unsubstituted phenylsulfone or substituted or unsubstituted phenoxy, or is cyano, nitro or halogen, R₈ is hydrogen, alkyl or alkoxy having 1 to 4 carbon atoms, substituted or unsubstituted phenoxy or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms, or R₈ is alkylsulfone having 1 to 4 carbon atoms, substituted or unsubstituted phenylsulfonic acid ester, cyano, nitro, halogen, substituted or unsubstituted carbalkoxy having 1 to 16 carbon atoms, or --P(O)(OT¹)₂, in which T¹ is as defined in claim 1, R.sub. 9 is hydrogen, unsubstituted or halogen-substituted alkyl having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 to 16 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted, or R₉ is --NQ₁ COT₁, in which Q₁ and T₁ are as defined in claim 1, or R₉ is alkylsulfone having 1 to 6 carbon atoms, phenylsulfone, hydroxyl, cyano, nitro or halogen, R₁₀ is hydrogen, alkyl having 1 to 4 carbon atoms or carbalkoxy having 2 to 13 carbon atoms, X₂ is hydrogen, alkyl or alkoxy, each having 1 to 6 carbon atoms, or --NL₂ COM₂, in which L₂ is hydrogen or alkyl having 1 to 4 carbon atoms and M₂ is substituted or unsubstituted alkyl or alkoxy having 1 to 18 carbon atoms, or X₂ is alkylsulfonylamino having 1 to 18 carbon atoms, or hydroxyl, Y₂ is hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 12 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 5 carbon atoms, or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety contains 1 to 6 carbon atoms and can be substituted, or Y₂ is substituted or unsubstituted phenylsulfonylamino or --NE₂ COG₂, in which E₂ is hydrogen or unsubstituted or cyano-substituted alkyl having 1 to 8 carbon atoms and G₂ is alkyl having 1 to 8 carbon atoms or substituted or unsubstituted alkoxy having 1 to 4 carbon atoms, or Y₂ is --NHP(O)(OG²)₂, in which G² is alkyl having 1 to 6 carbon atoms, or Y₂ is halogen or hydroxyl, Z₂ is hydrogen, alkyl having 1 to 12 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms or --NA₂ COD₂, in which A₂ is hydrogen or alkyl having 1 to 8 carbon atoms and D₂ is alkyl having 1 to 18 carbon atoms, or Z₂ is acyl having 2 to 7 carbon atoms, substituted or unsubstituted carbalkoxy having 2 to 19 carbon atoms, alkylsulfonylamino having 1 to 6 carbon atoms, halogen or the atoms which together with Y₂ form an unsubstituted or methyl-substituted 6-membered, saturated or unsaturated ring which can contain one or two hetero-atoms and W₂ is hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, or halogen.
 3. A colour-photographic recording material as claimed in claim 2, which contains a dye of the formula ##STR86## in which R₁₁ is hydrogen, alkyl having 1 to 12 carbon atoms which is substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 12 carbon atoms or is unsubstituted, alkoxy having 1 to 16 carbon atoms, a radical of the formula

    --O--(CH.sub.2).sub.m.sbsb.1 --OC.sub.2 H.sub.4 ].sub.n O--CH.sub.2).sub.m CH.sub.3,

in which m₁ is an integer from 2 to 16, n is 1 or 2 and m is an integer from 0 to 3, alkenyl having 2 to 4 carbon atoms, which is substituted by cyano and/or by carbalkoxy having 2 to 9 carbon atoms or is unsubstituted, aliphatic acyl having 2 or 3 carbon atoms, benzoyl which is substituted by chlorine, --CO₂ B₁, --SO₂ B₁ or --COB₁, in which B₁ is alkyl having 1 to 8 carbon atoms, or is unsubstituted, or R₁₁ is carbalkoxy having 2 to 16 carbon atoms, a radical of the formula ##STR87## in which m₁ and n are as defined above, or --NV₃ COU₂, in which V₃ is hydrogen and U₂ is unsubstituted or methoxy- or hydroxyl-substituted alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 4 carbon atoms, or R₁₁ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 10 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₁ is alkylsulfone having 1 to 8 carbon atoms, unsubstituted or substituted phenylsulfone, unsubstituted or substituted phenoxy, unsubstituted or substituted phenylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R₁₂ is hydrogen, unsubstituted or halogen-substituted alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR88## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 8 carbon atoms and can be substituted by methoxy, or R₁₂ is alkylsulfone having 1 to 6 carbon atoms, phenylsulfone or phenoxy which is unsubstituted or substituted by alkyl having 1 to 8 carbon atoms, or is cyano, nitro or halogen, R₁₃ is hydrogen, unsubstituted or fluorine-substituted alkyl having 1 or 2 carbon atoms, unsubstituted or methoxy-substituted alkoxy having 1 to 6 carbon atoms, carbalkoxy having 2 to 13 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, or R₁₃ is --NQ₂ COT₂, in which Q₂ is hydrogen and T₂ is alkyl having 1 to 4 carbon atoms, or R₁₃ is methylsulfone, phenylsulfone, hydroxyl, cyano, nitro or halogen X₃ is hydrogen, alkyl or alkoxy each having 1 to 4 carbon atoms, or --NL₃ COM₃, in which L₃ is hydrogen or methyl and M₃ is alkyl which has 1 to 18 carbon atoms and is unsubstituted or substituted by halogen, by carbalkoxy having 2 to 5 carbon atoms, by substituted or unsubstituted phenyl or phenoxy or by alkoxy having 1 to 5 carbon atoms, or X₃ is alkylsulfonylamino having 1 to 12 carbon atoms or hydroxyl, Y₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 12 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 to 5 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted by methoxy, by carbalkoxy having 2 to 5 carbon atoms, by acetoxy, by hydroxyl, by nitro, by cyano, by phenyl or by tosyl, or Y₃ is pyrrolidinyl, piperidinyl, morpholinyl or phenylsulfonylamino which is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, or Y₃ is --NE₃ COG₃, in which E₃ is hydrogen or unsubstituted or cyano-substituted alkyl having 1 to 4 carbon atoms and G₃ is alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 4 carbon atoms or a radical of the formula --O--(CH₂)_(k) --OC₂ H₄)_(n) OCH₃ in which k is an integer from 1 to 5 and n is as defined above, or Y₃ is ##STR89## in which G³ is alkyl having 1 to 4 carbon atoms, or Y₃ is halogen or hydroxyl, Z₃ is hydrogen, alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms, a radical of the formula --O--(CH₂)_(k).sbsb.1 --O--(CH₂)_(m) --CH₃ in which k₁ is an integer from 2 to 6 and m is as defined above, or Z₃ is --NA₃ COD₃, in which A₃ is hydrogen or alkyl having 1 to 4 carbon atoms and D₃ is alkyl having 1 to 12 carbon atoms, or Z₃ is acyl having 2 to 5 carbon atoms, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR90## in which k and n are as defined above, methylsulfonylamino, halogen or the atoms which together with Y₃ form an unsubstituted or methyl-substituted 6-membered saturated or unsaturated ring which contains nitrogen or nitrogen and oxygen, W₃ is hydrogen, alkyl or alkoxy each having 1 or 2 carbon atoms, or halogen, and R₈ and R₁₀ are as defined in claim
 2. 4. A colour-photographic recording material according to claim 3, which contains a dye of the formula ##STR91## in which R₁₄ is hydrogen, alkyl which has 1 to 12 carbon atoms and is unsubstituted or substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 7 carbon atoms, alkoxy having 1 to 12 carbon atoms, a radical of the formula --O(CH₂)_(m).sbsb.2 --OC₂ H₄)_(n) O(CH₂)_(m) CH₃ in which m₂ is an integer from 2 to B 12 and n and m are as defined in claim 3, or alkenyl which has 2 to 4 carbon atoms and is unsubstituted or substituted by cyano and/or by carbalkoxy having 2 to 7 carbon atoms, or R₁₄ is aliphatic acyl having 2 or 3 carbon atoms, or benzoyl which is unsubstituted or substituted by chlorine, --CO₂ B₂, --SO₂ B₂ or --COB₂, in which B₂ is alkyl having 1 to 4 carbon atoms, or R₁₄ is carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR92## in which m₃ is an integer from 2 to 8 and n is as defined above, or --NHCOU₃, in which U₃ is alkyl having 1 to 8 carbon atoms or alkenyl having 2 or 3 carbon atoms, or R₁₄ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₄ is alkylsulfone having 1 to 6 carbon atoms, unsubstituted or C₁₋₅ -alkyl-substituted or hydroxyl-substituted phenylsulfone or phenylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R₁₅ is hydrogen, unsubstituted or fluorine-substituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 or 2 carbon atoms, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR93## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, or R₁₅ is alkylsulfone having 1 to 4 carbon atoms or R₁₅ is cyano, nitro or halogen, R₁₆ is hydrogen, methyl, methoxy, or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, or R₁₆ is alkylsulfone having 1 to 4 carbon atoms, phenylsulfonic acid ester, cyano, nitro, halogen, unsubstituted or methoxy-substituted carbalkoxy having 1 to 12 carbon atoms or --P(O)(OT¹)₂, in which T¹ is as defined in claim 2, R₁₇ is hydrogen, methyl, trifluoromethyl, alkoxy having 1 to 4 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, or R₁₇ is --NHCOT₂, in which T₂ is as defined in claim 3, or R₁₇ is methylsulfone, phenylsulfone, hydroxyl, cyano, nitro or halogen, R₁₈ is hydrogen, methyl or carbalkoxy having 2 to 7 carbon atoms and X₃, Y₃, Z₃ and W₃ are as defined in claim
 3. 5. A colour-photographic recording material according to claim 4, which contains a dye of the formula ##STR94## in which X₄ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NL₄ COM₄, in which L₄ is hydrogen or methyl and M₄ is alkyl having 1 to 13 carbon atoms, or alkoxy having 1 to 4 carbon atoms, which can both be substituted by phenyl or phenoxy or by (C_(m).sbsb.3 H_(2m).sbsb.3₊₁ --C₆ H₄ -- or (C_(m).sbsb.3 H_(2m).sbsb.3₊₁ --C₆ H₄ --O-- or by fluorine, chlorine, alkoxy having 1 to 5 carbon atoms or by carbalkoxy having 2 or 3 carbon atoms, m₃ being as defined in claim 4, or X₄ is alkylsulfonylamino having 1 to 6 carbon atoms, or hydroxyl, Y₄ is hydrogen, alkyl having 1 or 2 carbon atoms, alkoxy having 1 to 8 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -- substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 6 carbon atoms and can be substituted by methoxy, carbalkoxy having 2 to 5 carbon atoms, acetoxy, hydroxyl, nitro, cyano or phenyl, or Y₄ is pyrrolidinyl, piperidinyl or phenylsulfonamino which can be substituted by alkyl having 1 to 4 carbon atoms, or Y₄ is --NE₃ COG₄, in which E₃ is as defined in claim 3, and G₄ is alkyl having 1 to 8 carbon atoms, alkoxy having 1 or 2 carbon atoms, or a radical of the formula --O--CH₂ --CH₂ --OC₂ H₄ OC₂ H₅ or --O--CH₂ --CH₂ --OC₂ ₄ --OCH₃, or Y₄ is ##STR95## in which G³ is as defined in claim 3, or Y₄ is halogen or hydroxyl, Z₄ is hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, --O(CH₂)_(k) --O(CH₂)_(m) --CH₃, in which k and m are as defined in claim 3, or --NA₄ COD₄, in which A₄ is hydrogen or methyl and D₄ is alkyl having 1 to 8 carbon atoms, or Z₄ is acetyl, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR96## in which k is as defined in claim 3, methylsulfonylamino, halogen or the atoms which together with Y₄ form ring systems such as ##STR97## W₄ is hydrogen, methyl, methoxy or halogen and R₁₄, R₁₅, R₁₆, R₁₇ and R₁₈ are as defined in claim
 4. 6. A colour-photographic recording material according to claim 5, which contains a dye of the formula ##STR98## in which R₁₉ is hydrogen, alkyl having 1 to 6 carbon atoms which can be substituted by alkoxy having 1 to 4 carbon atoms or by carbalkoxy having 2 to 7 carbon atoms, alkoxy having 1 to 8 carbon atoms, a radical of the formula --O--CH₂)_(m).sbsb.3 OC₂ H₄ --OCH₃ or --O--CH₂)_(m).sbsb.3 OC₂ H₄ --OC₂ H₅, in which m₃ is as defined in claim 4, vinyl which can be substituted by cyano and/or by carbalkoxy having 2 to 7 carbon atoms, acetyl, benzoyl which can be substituted in the para-position by chlorine, --CO₂ B₂, --SO₂ B₂ -- or --COB₂, in which B₂ is as defined in claim 4, carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR99## in which m₃ is as defined in claim 4, or --NHCOU₄, in which U₄ is alkyl having 1 to 4 carbon atoms or alkenyl having 2 or 3 carbon atoms, or R₁₉ is carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be substituted by methoxy, hydroxyl or amino, or R₁₉ is alkyl-sulfone having 1 to 6 carbon atoms or phenylsulfone or phenylsulfonic acid ester, which two radicals can be substituted in the para-position by alkyl having 1 to 5 carbon atoms or hydroxyl, or R₁₉ is hydroxyl, cyano, nitro, chlorine or bromine, R₂₀ is hydrogen, methyl, trifluoromethyl, methoxy, ethoxy, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR100## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, or R₂₀ is alkylsulfone having 1 to 4 carbon atoms, phenylsulfone or R₂₀ is cyano, nitro, chlorine or bromine, R₂₁ is hydrogen, methyl, methoxy, phenoxy or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 2 carbon atoms, or R₂₁ is alkylsulfone having 1 to 4 carbon atoms, cyano, nitro, bromine, chlorine or unsubstituted or methoxy-substituted carbalkoxy having 2 to 7 carbon atoms, or R₂₁ is --P(O)(OC₂ H₅)₂, R₂₂ is hydrogen, methyl, trifluoromethyl, unsubstituted or methoxy-substituted alkoxy having 1 to 2 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be substituted by methoxy, or R₂₂ is --NHCOT₂, in which T₂ is as defined in claim 4, or R₂₂ is methylsulfone, phenylsulfone, hydroxyl, cyano, chlorine or bromine, R₂₃ is hydrogen, methyl or carbalkoxy having 2 or 3 carbon atoms, X₅ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NL₅ -COM₅, in which L₅ is hydrogen and M₅ is alkyl having 1 to 8 carbon atoms, or alkoxy having 1 or 2 carbon atoms, which radicals can be substituted by fluorine, chlorine, alkoxy having 1 to 5 carbon atoms, carbalkoxy having 2 or 3 carbon atoms, phenyl, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --, phenoxy, or para-C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O--, m₃ being as defined in claim 4, or X₅ is alkylsulfonylamino having 1 to 6 carbon atoms, or hydroxyl, W₅ is hydrogen, methyl, methoxy or chlorine and Y₄ and Z₄ are as defined in claim
 5. 7. A colour-photographic recording material as claimed in claim 6, which contains a dye of the formula ##STR101## in which R₂₄ is hydrogen or alkyl having 1 to 4 carbon atoms, which can be substituted by carbalkoxy having 2 to 7 carbon atoms, or R₂₄ is alkoxy having 1 to 4 carbon atoms, a radical of the formula --O--(CH₂)_(k) --OC₂ H₄ --OCH₃ or --O--(CH₂)_(k) --OC₂ H₄ --OC₂ H₅, in which k is as defined in claim 3, carbalkoxy having 2 to 9 carbon atoms, a radical of the formula ##STR102## in which m₃ is as defined in claim 4, --NHCOU₄, in which U₄ is as defined in claim 6, carboxamido or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1, 2 or 3 carbon atoms and can be substituted by methoxy, or R₂₄ is alkylsulfone having 1 to 6 carbon atoms or is phenylsulfone or phenylsulfonic acid ester, each of which two radicals can be substituted in the para-position by alkyl having 1 to 5 carbon atoms or hydroxyl, or R₂₄ is hydroxyl, nitro, chlorine or bromine, R₂₅ is hydrogen, methyl, methoxy, ethoxy, carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR103## or N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be substituted by methoxy, or R₂₅ is alkylsulfone having 1 to 4 carbon atoms or R₂₅ is cyano, nitro, chlorine or bromine, R₂₆ is hydrogen, cyano, chlorine or bromine, R₂₇ is hydrogen or alkoxy having 1 or 2 carbon atoms, or R₂₇ is carbalkoxy having 2 to 9 carbon atoms, --NHCOT₂, in which T₂ is as defined in claim 6, hydroxyl or chlorine, R₂₈ is hydrogen or carbalkoxy having 2 or 3 carbon atoms, X₆ is hydrogen, alkyl having 1 to 4 carbon atoms, methoxy or --NHCOM₆, in which M₆ is alkyl having 1 to 4 carbon atoms which is optionally substituted by alkoxy having 1 to 5 carbon atoms, by phenoxy or para-(C_(k) H_(2k+1))--C₆ H₄ --O--, k being as defined in claim 3, or X₆ is hydroxyl, Y₅ is hydrogen, alkoxy having 1 to 4 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -- substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, carbalkoxy having 2 or 3 carbon atoms, acetoxy, hydroxyl, cyano or phenyl, or Y₅ is --NE₃ COG₄, in which E₃ and G₄ are as defined in claim 5, or Y₅ is hydroxyl, Z₅ is hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, acetyl, carbalkoxy having 2 to 5 carbon atoms, a radical of the formula ##STR104## in which k is as defined in claim 3, --NA₄ COD₄, in which A₄ and D₄ are as defined in claim 5, or chlorine, and W₅ is as defined in claim
 6. 8. A colour-photographic recording material according to claim 7, which contains a dye of the formula ##STR105## in which R₂₉ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, carbalkoxy having 2 to 9 carbon atoms or a radical of the formula ##STR106## in which m₃ is as defined in claim 7, R₃₀ is hydrogen, methyl, methoxy, cyano, chlorine or bromine, R₃₁ is hydrogen or bromine, R₃₂ is hydrogen or chlorine, R₃₃ is hydrogen or carbomethoxy, X₇ is ##STR107## in which M₇ is alkyl having 1 to 4 carbon atoms, or X₇ is hydroxyl, Y₆ is hydrogen, N-alkyl-substituted amino, in which the alkyl moiety has 1 or 2 carbon atoms and can be cyano-substituted, or --NE₃ COG₄, in which E₃ and G₄ are as defined in claim 5, Z₆ is hydrogen or alkoxy having 1 to 4 carbon atoms and W₆ is hydrogen or methyl.
 9. A colour-photographic recording material according to claim 8, which contains a dye of one of the formulae ##STR108##
 10. A colour-photographic recording material according to claim 6, which contains a dye of the formula ##STR109## in which R₃₄ is hydrogen or alkyl having 1 or 2 carbon atoms, which can be substituted by carbalkoxy having 2 or 3 carbon atoms, or is carbalkoxy having 2 or 3 carbon atoms, a radical of the formula ##STR110## or vinyl which can be substituted by cyano and/or carbalkoxy having 2 to 5 carbon atoms, or R₃₄ is N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 3 carbon atoms and can be methoxy-substituted, alkylsulfone having 1 to 6 carbon atoms, phenylsulfonic acid ester, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O--SO₂ --, in which m₃ is as defined in claim 4, cyano, nitro, chlorine or bromine, R₃₅ is hydrogen, trifluoromethyl, carbalkoxy having 2 or 3 carbon atoms, alkylsulfone having 1 to 4 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 4 carbon atoms and can be methoxy-substituted, cyano, nitro, chlorine or bromine, R₃₆ is hydrogen, methylsulfone, N,N-diethylsulfonamide, cyano, nitro, chlorine or bromine, R₃₇ is hydrogen, methyl, carbalkoxy having 2 to 7 carbon atoms, N,N-dialkyl-substituted sulfonamido or carboxamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, cyano or chlorine, R₃₈ is hydrogen or methyl, X₈ is hydrogen, methyl or --NHCOM₇, in which M₇ is alkyl having 1 to 8 carbon atoms which is unsubstituted or substituted by carbalkoxy having 2 or 3 carbon atoms, fluorine, chlorine, phenyl, phenoxy, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ -- or para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ O--, or X₈ is alkylsulfonylamino having 1 to 6 carbon atoms, or hydroxyl, Y₇ is alkyl having 1 or 2 carbon atoms, alkoxy having 1 to 8 carbon atoms, unsubstituted or --OC₂ H₄ --OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms, or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, carbomethoxy, acetoxy, cyano, hydroxyl or phenyl, or Y₇ is --NHCOG₅, in which G₅ is alkyl having 1 to 4 carbon atoms, and Z₇ is hydrogen, alkoxy having 1 to 2 carbon atoms, a radical of the formula --OCH₂ CH₂ --O(CH₂)_(m) --CH₃, in which m is as defined in claim 5, --NHCOD₄, in which D₄ is as defined in claim 5, or chlorine,
 11. A colour-photographic recording material according to claim 10, which contains a dye of the formula ##STR111## in which R₃₉ is hydrogen or alkyl having 1 to 2 carbon atoms, which can be substituted by carbalkoxy having 2 or 3 carbon atoms, or R₃₉ is carbalkoxy having 2 or 3 carbon atoms, alkylsulfone having 1 to 6 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 3 carbon atoms and can be methoxy-substituted, cyano, nitro, chlorine or bromine, R₄₀ is hydrogen, alkylsulfone having 1 to 4 carbon atoms, N,N-dimethylsulfonamide or N,N-diethylsulfonamide, cyano or nitro, R₄₁ is hydrogen, methylsulfone, cyano or nitro, R₄₂ is hydrogen or cyano, X₉ is methyl or ##STR112## in which M₈ is alkyl having 1 to 4 carbon atoms, or X₉ is hydroxyl, Y₈ is alkoxy having 1 to 8 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, acetoxy or cyano, and Z₈ is hydrogen, alkoxy having 1 or 2 carbon atoms, a radical of the formula --OCH₂ CH₂ --O(CH₂)_(m) --CH₃, in which m is as defined in claim 3, or --NHCOD₄, in which D₄ is as defined in claim
 10. 12. A colour-photographic recording material according to claim 11, which contains a dye of one of the formulae ##STR113##
 13. A colour-photographic recording material according to claim 6, which contains a dye of the formula ##STR114## in which R₄₃ is vinyl which can be substituted by cyano and/or carbalkoxy having 2 to 7 carbon atoms, or R₄₃ is carbalkoxy having 2 or 3 carbon atoms, N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 to 5 carbon atoms and can be methoxy-, amino- or hydroxyl-substituted, alkylsulfone having 1 to 6 carbon atoms, phenylsulfonic acid ester, para-(C_(m).sbsb.3 H_(2m).sbsb.3₊₁)--C₆ H₄ --O--SO₂ --, in which m₃ is as defined in claim 10, cyano or nitro, R₄₄ is N,N-dimethylsulfonamido or N,N-diethylsulfonamido, cyano, nitro, chlorine, bromine, methylsulfone or trifluoromethyl, R₄₆ is hydrogen or carbalkoxy having 2 to 6 carbon atoms, X₁₀ is methyl ##STR115## in which M₅ is as defined in claim 6, or alkylsulfonamide having 1 to 6 carbon atoms, Y₉ is unsubstituted or --OC₂ H₄ -OCH₃ -substituted carbalkoxy having 2 or 3 carbon atoms or N-alkyl-substituted or N,N-dialkyl-substituted amino, in which each alkyl moiety has 1 to 4 carbon atoms and can be substituted by methoxy, acetoxy, cyano, hydroxyl or phenyl, and Z₉ is hydrogen, methoxy, --OCH₂ -CH₂ -OC₂ H₅, or --OCH₂ CH₂ -OCH₃.
 14. A colour-photographic recording material according to claim 13, which contains a dye of the formula ##STR116## in which R₄₇ is vinyl which can be substituted by cyano and/or carbalkoxy having 2 or 3 carbon atoms, or R₄₇ is N-alkyl-substituted or N,N-dialkyl-substituted sulfonamido, in which each alkyl moiety has 1 or 2 carbon atoms and can be methoxy-substituted, cyano or nitro, R₄₈ is cyano, trifluoromethyl or nitro, X₁₁ is ##STR117## in which M₈ is as defined in claim 11, and Y₁₀ is dimethylamino or diethylamino.
 15. A colour-photograhic recording material according to claim 14, which contains a dye of one of the formulae ##STR118##
 16. A process for the preparation of a colour-photographic recording material for the silver dye bleach process, which comprises incorporating at least one non-diffusible, bleachable and oil-soluble monoazo dye of the formula (1) in claim 1 dissolved in a high-boiling organic solvent into at least one silver halide emulsion layer or into a colloid layer adjacent to the silver halide emulsion layer.
 17. A photographic image produced with the colour-photographic recording material according to claim
 1. 